Hydrogenated block copolymer, vibration damper, sound insulator, interlayer for laminated glass, dam rubber, shoe sole material, flooring material, laminate, and laminated glass

ABSTRACT

Provided is a hydrogenated block copolymer, which is a hydrogenation product of a block copolymer including a polymer block (A) containing more than 70 mol % of a structural unit derived from an aromatic vinyl compound and a polymer block (B) containing 30 mol % or more of a structural unit derived from at least one selected from the group consisting of a conjugated diene compound and isobutylene, the hydrogenated block copolymer being satisfied with the following requirements (1) and (2): 
     Requirement (1): the content of the polymer block (A) in the block copolymer is 1 to 30% by mass; and 
     Requirement (2): when the polymer block (B) is regarded as having a structure with a hydrogenation rate of 100 mol %, an average value of a methylene chain length of a main chain of the structural unit derived from at least one selected from the group consisting of a conjugated diene compound and isobutylene is 1.0 to 6.0.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation application of prior U.S. applicationSer. No. 16/301,592, filed Nov. 14, 2018, the disclosure of which isincorporated herein by reference in its entirety. U.S. application Ser.No. 16/301,592 is the National Stage of PCT/JP2017/018444, filed May 17,2017, the disclosure of which is incorporated herein by reference in itsentirety. U.S. application Ser. No. 16/301,592 claims priority toJapanese Application No. 2016-100000, filed May 18, 2016, and toJapanese Application No. 2016-245931, filed Dec. 19, 2016, thedisclosures of which are incorporated herein by reference in theirentireties.

TECHNICAL FIELD

The present invention relates to a hydrogenated block copolymer, avibration damping material, a sound insulator, an intermediate film forlaminated glass, a dam rubber, a shoe sole material, a flooringmaterial, a laminate, and a laminated glass.

BACKGROUND ART

Hitherto, in the case of executing a glass in a place where soundinsulation is required, such as a window, there has been adopted amethod in which the thickness of glass is made thick to enhance a soundinsulation effect due to the weight, or a method in which a soundinsulation effect is enhanced by using a laminated glass obtained bylaminating two or more glass sheets and an intermediate film. Accordingto the latter method using an intermediate film, the sound insulationproperties of glass are improved by a damping performance of theintermediate film and a performance of the intermediate film forconverting vibration energy into thermal energy.

As for the method of improving the sound insulation properties, anintermediate film in which a copolymer of polystyrene and a rubber-basedresin is laminated by a plasticized polyvinyl acetal-based resin isproposed (see, for example, PTL 1).

In addition, an intermediate film for laminated glass composed ofpolyvinyl butyral and having certain impact resistance and soundinsulation properties and a laminated glass are proposed (see, forexample, PTL 2).

Furthermore, in recent years, from the viewpoint of energy saving, animprovement of fuel consumption of an automobile or the like has beenbecoming a big issue more and more. Examples of the method of improvingthe fuel consumption of an automobile or the like include a method ofcontrolling the use of an air conditioner; and a method of reducing theweight of an automobile.

Examples of the method of controlling the use of an air conditionerinclude a method in which a laminated glass with high heat insulationproperties capable of controlling a temperature rise within theautomobile is used for a window glass of an automobile. Examples of adevice of reducing the weight of an automobile include a method ofreducing the weight of a window glass or a steel sheet.

In order to reduce the weight of a window glass, it is necessary to makethe laminated glass thin. In order to reduce the weight of a steelsheet, there is a method in which the thickness of the sheet is madethin, or the steel is replaced by aluminum or a resin. However, in allof the cases, there is involved such a problem that lightening resultsin a lowering of the sound insulation properties.

As a method of producing a laminated glass having suitable soundinsulation properties, a method in which a layer containing a copolymerof styrene and a rubber-based resin monomer is sandwiched by layerscontaining a heat adhesive resin to form an intermediate film having athree-layer configuration, and the intermediate film is laminated withtwo or more sheets of glass to produce a laminated glass (see, forexample, PTL 3); and a method in which a laminated glass is produced byusing a laminate with improved interlayer adhesiveness, which isobtained by laminating a layer containing a polyvinyl acetal and a layercontaining a polyolefin (see, for example, PTL 4) are proposed.

CITATION LIST Patent Literature

PTL 1: JP 2007-91491 A

PTL 2: WO 2005/018969 A

PTL 3: JP 2009-256128 A

PTL 4: JP 2012-6406 A

SUMMARY OF INVENTION Technical Problem

But, in all of the background arts, there was involved such a problemthat in the case of making the laminated glass thin, the soundinsulation properties become insufficient. In addition, in a laminatedglass, an adhesive auxiliary layer (also referred to as “skin layer”) isfrequently provided between the glass and the intermediate film, andtherefore, the intermediate film is also required to have low shrinkingproperties. Furthermore, the intermediate film is required to havetransparency, and in view of the matter that a wrinkle to be caused dueto shrinkage appears to become uneven is problematic, the intermediatefilm is required to have low shrinking properties, too.

Then, a problem of the present invention is to provide a hydrogenatedblock copolymer capable of enhancing the sound insulation properties inlaminated glasses of any thickness and to provide a vibration dampingmaterial, a sound insulator, an intermediate film for laminated glasswith low shrinking properties, a dam rubber, a shoe sole material, aflooring material, a laminate, and a laminated glass, each of which isobtained by using the foregoing hydrogenated block copolymer.

Solution to Problem

In order to solve the aforementioned problem, the present inventors madeextensive and intensive investigations. As a result, it has become clearthat as a cause that the sound insulation properties becomeinsufficient, a possibility that a relation between a frequency at whicha sound transmission loss (STL) is lowered due to a coincidence effect(namely, a phenomenon in which bending vibration of a rigid material,such as a glass, and vibration of incident sonic waves coincidentallycause a resonant state) and a peak frequency of tan δ of a hydrogenatedblock copolymer gives a large influence is high. Furthermore, it hasbecome clear that by reducing the degree of a lowering of STL per se andincreasing a lowest frequency at which the coincidence effect isgenerated (a so-called coincidence critical frequency), the soundinsulation properties in a low frequency region become much moreexcellent.

Then, by regulating these [(1) the relation between the frequency atwhich STL is lowered due to the coincidence effect and the peakfrequency of tan δ of a hydrogenated block copolymer, (2) a reduction ofthe degree of a lowering of STL, and (3) an increase of a coincidencecritical frequency], the present inventors made the development of amaterial capable of efficiently enhancing the sound insulationproperties even when used for laminated glasses of any thickness.Specifically, it has become clear that the aforementioned problem can besolved by a hydrogenated block copolymer that is a hydrogenation productof a block copolymer including a polymer block (A) containing apredetermined amount of a structural unit derived from an aromatic vinylcompound and a polymer block (B) containing a predetermined amount of astructural unit derived from at least one selected from the groupconsisting of a conjugated diene compound and isobutylene, thehydrogenated block copolymer being satisfied with specifiedrequirements, thereby leading to the present invention.

The present invention is concerned with the following [1] to [29].

[1] A hydrogenated block copolymer, which is a hydrogenation product ofa block copolymer including a polymer block (A) containing more than 70mol % of a structural unit derived from an aromatic vinyl compound and apolymer block (B) containing 30 mol % or more of a structural unitderived from at least one selected from the group consisting of aconjugated diene compound and isobutylene, the hydrogenated blockcopolymer being satisfied with the following requirements (1) and (2):

Requirement (1): the content of the polymer block (A) in the blockcopolymer is from 1 to 30% by mass; and

Requirement (2): when the polymer block (B) is regarded as having astructure with a hydrogenation rate of 100 mol %, an average value of amethylene chain length of a main chain of the structural unit derivedfrom at least one selected from the group consisting of a conjugateddiene compound and isobutylene is from 1.0 to 6.0.

[2] The hydrogenated block copolymer as set forth in the above [1],wherein the hydrogenation rate in the polymer block (B) is from 80 to 99mol %.

[3] The hydrogenated block copolymer as set forth in the above [1] or[2], wherein when the polymer block (B) is regarded as having astructure with a hydrogenation rate of 100 mol %, an average value of asubstituent constant (ν) of a side chain which the main chain has perethylene unit is from 0.25 to 1.1.[4] The hydrogenated block copolymer as set forth in any of the above[1] to [3], wherein when the polymer block (B) is regarded as having astructure with a hydrogenation rate of 100 mol %, an average value of asubstituent constant (ν) of a side chain which the main chain has perethylene unit is from 0.30 to 0.55.[5] The hydrogenated block copolymer as set forth in any of the above[1] to [4], wherein the conjugated diene compound is isoprene,butadiene, or a mixture of isoprene and butadiene.[6] The hydrogenated block copolymer as set forth in any of the above[1] to [5], wherein the conjugated diene compound is isoprene.[7] The hydrogenated block copolymer as set forth in any of the above[1] to [6], wherein in the requirement (1), the content of the polymerblock (A) in the block copolymer is from 3.5 to 4.5% by mass.[8] The hydrogenated block copolymer as set forth in any of the above[1] to [7], wherein in the requirement (2), an average value of amethylene chain length of a main chain of the structural unit derivedfrom the conjugated diene compound is from 1.5 to 3.0.[9] The hydrogenated block copolymer as set forth in any of the above[1] to [8], which exhibits a peak top intensity of tan δ, as measuredunder a condition at a strain amount of 0.1%, a frequency of 1 Hz, ameasurement temperature of −70 to 200° C., and a temperature rise rateof 3° C./min in conformity of JIS K7244-10 (2005), of 0.5 or more.The hydrogenated block copolymer as set forth in any of the above [1] to[9], wherein a morphology of a film having a thickness of 1 mm, which isobtained by molding the copolymer under the following molding condition,has a microphase-separated structure of a sphere or cylinder:

Molding condition: to apply a pressure at a temperature of 230° C. undera pressure of 10 MPa for 3 minutes.

[11] The hydrogenated block copolymer as set forth in any of the above[1] to [10], wherein a morphology of a film having a thickness of 1 mm,which is obtained by molding the copolymer under the following moldingcondition, has a microphase-separated structure of a sphere:

Molding condition: to apply a pressure at a temperature of 230° C. undera pressure of 10 MPa for 3 minutes.

[12] The hydrogenated block copolymer as set forth in any of the above[1] to [11], wherein a shrinkage factor in the MD direction as definedbelow is 15% or less:

Shrinkage factor in the MD direction: after stationarily placing aribbon sheet (MD/TD=4.0 cm/3.5 cm, 1 mm) obtained by extrusion moldingthe copolymer under an unstretched condition at 230° C. on talc at 230°C. for one week, when the length in the MD direction is taken as y, andan initial length (4.0 cm) in the MD direction is taken as x, theshrinkage factor in the MD direction is defined as {(x−y)/x}×100(%).

[13] A vibration damping material containing the hydrogenated blockcopolymer as set forth in any of the above [1] to [12].

[14] A sound insulator containing the hydrogenated block copolymer asset forth in any of the above [1] to [12].

[15] An intermediate film for laminated glass containing thehydrogenated block copolymer as set forth in any of the above [1] to[12].

[16] The intermediate film for laminated glass as set forth in the above[15] containing the hydrogenated block copolymer as set forth in any ofthe above [1] to [12], provided that a peak top temperature of tan δ asmeasured with respect to a sheet-shaped test piece having a thickness of1.0 mm, which is obtained by molding the copolymer according to thefollowing molding condition, under a condition at a strain amount of0.1%, a frequency of 1 Hz, a measurement temperature of −70 to 200° C.,and a temperature rise rate of 3° C./min in conformity of JIS K7244-10(2005) is −40 to 35° C.:

Molding condition: to apply a pressure at a temperature of 230° C. undera pressure of 10 MPa for 3 minutes.

[17] A dam rubber containing the hydrogenated block copolymer as setforth in any of the above [1] to [12].

[18] A shoe sole material containing the hydrogenated block copolymer asset forth in any of the above [1] to [12].

[19] A flooring material containing the hydrogenated block copolymer asset forth in any of the above [1] to [12].

[20] A laminate including an X layer containing the hydrogenated blockcopolymer as set forth in any of the above [1] to [12] and a Y layerlaminated on at least one surface of the X layer.

[21] The laminate as set forth in the above [20], which is a laminateincluding the X layer and a plurality of the Y layers, in which the Xlayer being laminated between at least two Y layers, and which issatisfied with the following formula (I).200≤(peak top frequency of tan δ)×√{square root over(B/m)}≤2,000,000  (I)

In the formula (I), B represents a bending stiffness (Pa·m³) per unitwidth of the laminate; m represents a surface density (kg/m²) of thelaminate; and the peak top frequency (Hz) of tan δ represents afrequency when a peak of tan δ of the hydrogenated block copolymerdetermined according to the following method becomes maximum.

Measurement method of peak top frequency of tan δ: by using asheet-shaped test piece having a thickness of 1.0 mm, which is obtainedby molding the copolymer according to the following molding condition, amaster curve calculated by the WLF method is prepared on the basis ofmeasured values as measured under a condition at a strain amount of0.1%, a frequency of 1 to 100 Hz, and a measurement temperature of 20°C., 10° C., 0° C., −10° C., and −30° C., respectively in conformity ofJIS K7244-10 (2005), to determine the peak top frequency.

Molding condition: to apply a pressure at a temperature of 230° C. undera pressure of 10 MPa for 3 minutes.

[22] The laminate as set forth in the above [20] or [21], wherein the Ylayer, or at least one of the plural Y layers is a glass layer.

[23] The laminate as set forth in the above [22], wherein a thickness ofthe glass layer is from 0.5 to 5 mm.

[24] The laminate as set forth in any of the above [20] to [23], whereinat least one of the plural Y layers is a layer containing athermoplastic resin (i) different from the hydrogenated block copolymeras set forth in any of the above [1] to [12].

[25] The laminate as set forth in the above [24], wherein thethermoplastic resin (i) is a polyvinyl acetal resin.

[26] The laminate as set forth in the above [24], wherein thethermoplastic resin (i) is an ionomer.

[27] The laminate as set forth in any of the above [24] to [26], whichis a laminate of a glass layer, a layer containing the thermoplasticresin (i), the X layer, a layer containing the thermoplastic resin (i),and a glass layer in this order.

[28] A laminated glass including the laminate as set forth in any of theabove [20] to [27].

[29] The laminated glass as set forth in the above [28], which is awindow shield for automobile, a side glass for automobile, a sunroof forautomobile, a rear glass for automobile, or a glass for head-up display.

Advantageous Effects of Invention

In accordance with the present invention, it is possible to provide ahydrogenated block copolymer capable of enhancing the sound insulationproperties in laminated glasses of any thickness as well as a vibrationdamping material, a sound insulator, an intermediate film for laminatedglass with low shrinking properties, a dam rubber, a shoe sole material,a flooring material, a laminate, and a laminated glass, each of which isobtained by using the foregoing hydrogenated block copolymer.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a diagrammatic view of a microphase-separated structure of asphere.

FIG. 2 is a diagrammatic view of a microphase-separated structure of acylinder.

FIG. 3 is a diagrammatic view of a microphase-separated structure of alamella.

FIG. 4A is a graph showing a relation between a frequency and a soundtransmission loss of each of laminates 3 and 4 in Example 1.

FIG. 4B is a graph showing a relation between a frequency and tan δ of ahydrogenated block copolymer used in Example 1.

FIG. 5A is a graph showing a relation between a frequency and a soundtransmission loss of each of laminates 3 and 4 in Example 2.

FIG. 5B is a graph showing a relation between a frequency and tan δ of ahydrogenated block copolymer used in Example 2.

FIG. 6A is a graph showing a relation between a frequency and a soundtransmission loss of each of laminates 3 and 4 in Example 3.

FIG. 6B is a graph showing a relation between a frequency and tan δ of ahydrogenated block copolymer used in Example 3.

FIG. 7A is a graph showing a relation between a frequency and a soundtransmission loss of each of laminates 3 and 4 in Example 4.

FIG. 7B is a graph showing a relation between a frequency and tan δ of ahydrogenated block copolymer used in Example 4.

FIG. 8A is a graph showing a relation between a frequency and a soundtransmission loss of each of laminates 3 and 4 in Example 5.

FIG. 8B is a graph showing a relation between a frequency and tan δ of ahydrogenated block copolymer used in Example 5.

FIG. 9A is a graph showing a relation between a frequency and a soundtransmission loss of each of laminates 3 and 4 in Example 6.

FIG. 9B is a graph showing a relation between a frequency and tan δ of ahydrogenated block copolymer used in Example 6.

FIG. 10A is a graph showing a relation between a frequency and a soundtransmission loss of each of laminates 3 and 4 in Example 7.

FIG. 10B is a graph showing a relation between a frequency and tan δ ofa hydrogenated block copolymer used in Example 7.

FIG. 11A is a graph showing a relation between a frequency and a soundtransmission loss of each of laminates 3 and 4 in Example 8.

FIG. 11B is a graph showing a relation between a frequency and tan δ ofa hydrogenated block copolymer used in Example 8.

FIG. 12A is a graph showing a relation between a frequency and a soundtransmission loss of each of laminates 3 and 4 in Example 9.

FIG. 12B is a graph showing a relation between a frequency and tan δ ofa hydrogenated block copolymer used in Example 9.

FIG. 13A is a graph showing a relation between a frequency and a soundtransmission loss of each of laminates 3 and 4 in Example 10.

FIG. 13B is a graph showing a relation between a frequency and tan δ ofa hydrogenated block copolymer used in Example 10.

FIG. 14A is a graph showing a relation between a frequency and a soundtransmission loss of each of laminates 3 and 4 in Example 11.

FIG. 14B is a graph showing a relation between a frequency and tan δ ofa hydrogenated block copolymer used in Example 11.

FIG. 15A is a graph showing a relation between a frequency and a soundtransmission loss of each of laminates 3 and 4 in Example 12.

FIG. 15B is a graph showing a relation between a frequency and tan δ ofa hydrogenated block copolymer used in Example 12.

FIG. 16A is a graph showing a relation between a frequency and a soundtransmission loss of each of laminates 3 and 4 in Example 13. FIG. 16(b)is a graph showing a relation between a frequency and tan δ of ahydrogenated block copolymer used in Example 13.

FIG. 17A is a graph showing a relation between a frequency and a soundtransmission loss of each of laminates 3 and 4 in Example 14.

FIG. 17B is a graph showing a relation between a frequency and tan δ ofa hydrogenated block copolymer used in Example 14.

FIG. 18A is a graph showing a relation between a frequency and a soundtransmission loss of each of laminates 3 and 4 in Example 15.

FIG. 18B is a graph showing a relation between a frequency and tan δ ofa hydrogenated block copolymer used in Example 15.

FIG. 19A is a graph showing a relation between a frequency and a soundtransmission loss of each of laminates 3 and 4 in Example 16.

FIG. 19B is a graph showing a relation between a frequency and tan δ ofa hydrogenated block copolymer used in Example 16.

FIG. 20A is a graph showing a relation between a frequency and a soundtransmission loss of each of laminates 3 and 4 in Comparative Example 1.

FIG. 20B is a graph showing a relation between a frequency and tan δ ofa hydrogenated block copolymer used in Comparative Example 1.

FIG. 21A is a graph showing a relation between a frequency and a soundtransmission loss of each of laminates 3 and 4 in Comparative Example 2.

FIG. 21B is a graph showing a relation between a frequency and tan δ ofa hydrogenated block copolymer used in Comparative Example 2.

FIG. 22A is a graph showing a relation between a frequency and a soundtransmission loss of each of laminates 3 and 4 in Comparative Example 3.

FIG. 22B is a graph showing a relation between a frequency and tan δ ofa hydrogenated block copolymer used in Comparative Example 3.

FIG. 23A is a graph showing a relation between a frequency and a soundtransmission loss of each of laminates 3 and 4 in Comparative Example 5.

FIG. 23B is a graph showing a relation between a frequency and tan δ ofa hydrogenated block copolymer used in Comparative Example 5.

DESCRIPTION OF EMBODIMENTS

[Hydrogenated Block Copolymer]

The present invention is concerned with a hydrogenated block copolymerthat is a hydrogenation product of a block copolymer including a polymerblock (A) containing more than 70 mol % of a structural unit derivedfrom an aromatic vinyl compound and a polymer block (B) containing 30mol % or more of a structural unit derived from at least one selectedfrom the group consisting of a conjugated diene compound andisobutylene, the hydrogenated block copolymer being satisfied with thefollowing requirements (1) and (2):

Requirement (1): the content of the polymer block (A) in the blockcopolymer is 1 to 30% by mass; and

Requirement (2): when the polymer block (B) is regarded as having astructure with a hydrogenation rate of 100 mol %, an average value of amethylene chain length of a main chain of the structural unit derivedfrom at least one selected from the group consisting of a conjugateddiene compound and isobutylene is 1.0 to 6.0.

So long as the hydrogenated block copolymer of the present invention isconcerned, in in laminated glasses of any thickness, and particularly,even in laminated glasses using a thin glass (for example, the thicknessis 2.5 mm or less), the sound insulation properties can be efficientlyenhanced. As for this matter, it may be conjectured that the relationbetween a frequency at which a sound transmission loss (STL) is lowereddue to a coincidence effect and a peak frequency of tan δ of thehydrogenated block copolymer could be regulated, and furthermore, as thecase may be, the degree of a lowering of the sound transmission loss perse could be reduced, and the lowest frequency at which the coincidenceeffect is generated (a so-called coincidence critical frequency) couldbe increased.

The hydrogenated block copolymer of the present invention is hereunderdescribed in detail.

The hydrogenated block copolymer of the present invention is ahydrogenation product of a block copolymer including the aforementionedpolymer block (A) and polymer block (B).

(Polymer Block (A))

The polymer block (A) contains more than 70 mol % of a structural unitderived from an aromatic vinyl compound (hereinafter sometimesabbreviated as “aromatic vinyl compound unit”), and from the viewpointof mechanical characteristics, the content of the aromatic vinylcompound unit is preferably 80 mol % or more, more preferably 85 mol %or more, still more preferably 90 mol % or more, especially preferably95 mol % or more, and substantially 100 mol %.

Examples of the aforementioned aromatic vinyl compound include styrene,o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene,β-methylstyrene, 2,6-dimethylstyrene, 2,4-dimethylstyrene,α-methyl-o-methylstyrene, α-methyl-m-methylstyrene,α-methyl-p-methylstyrene, β-methyl-o-methylstyrene,β-methyl-m-methylstyrene, β-methyl-p-methylstyrene,2,4,6-trimethylstyrene, α-methyl-2,6-dimethylstyrene,α-methyl-2,4-dimethylstyrene, β-methyl-2,6-dimethylstyrene,β-methyl-2,4-dimethylstyrene, o-chlorostyrene, m-chlorostyrene,p-chlorostyrene, 2,6-dichlorostyrene, 2,4-dichlorostyrene,α-chloro-o-chlorostyrene, α-chloro-m-chlorostyrene,α-chloro-p-chlorostyrene, β-chloro-o-chlorostyrene,β-chloro-m-chlorostyrene, β-chloro-p-chlorostyrene,2,4,6-trichlorostyrene, α-chloro-2,6-dichlorostyrene,α-chloro-2,4-dichlorostyrene, β-chloro-2,6-dichlorostyrene,β-chloro-2,4-dichlorostyrene, o-t-butylstyrene, m-t-butylstyrene,p-t-butylstyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene,o-chloromethylstyrene, m-chloromethylstyrene, p-chloromethylstyrene,o-bromostyrene, m-bromostyrene, p-bromostyrene, a styrene derivativesubstituted with a silyl group, indene, and vinylnaphthalene. Thesearomatic vinyl compounds may be used alone or may be used in combinationof two or more thereof. Above all, from the viewpoint of productioncosts and balance in physical properties, styrene, α-methylstyrene,p-methylstyrene, and a mixture thereof are preferred, with styrene beingmore preferred.

However, the polymer block (A) may contain a structural unit derivedfrom an unsaturated monomer other than the aromatic vinyl compound(hereinafter sometimes abbreviated as “other unsaturated monomer unit”)in a proportion of 30 mol % or less so long as the object and effects ofthe present invention are not impaired. As the other unsaturatedmonomer, for example, at least one selected from the group consisting ofbutadiene, isoprene, 2,3-dimethylbutadiene, 1,3-pentadiene,1,3-hexadiene, isobutylene, methyl methacrylate, methyl vinyl ether,N-vinylcarbazole, β-pinene, 8,9-p-menthene, dipentene, methylenenorbornene, and 2-methylenetetrahydrofuran is exemplified. The bondingmode in the case where the polymer block (A) contains the otherunsaturated monomer unit is not particularly limited, and may be eitherrandom or tapered.

The content of the structural unit derived from the aforementioned otherunsaturated monomer in the polymer block (A) is preferably 10 mol % orless, more preferably 5 mol % or less, and still more preferably 0 mol%.

The block copolymer may include at least one aforementioned polymerblock (A). In the case where the block copolymer includes two or morepolymer blocks (A), those polymer blocks (A) may be the same as ordifferent from each other. In this specification, the wording “differentpolymer blocks” means that at least one of the monomer unitsconstituting the polymer block, the weight average molecular weight, thestereoregularity, and in the case where the block contains pluralmonomer units, the ratio of the monomer units and the copolymerizationmode (random, gradient, or block) differs between the blocks.

Though the weight average molecular weight (Mw) of the aforementionedpolymer block (A) which the block copolymer has is not particularlylimited, the weight average molecular weight of at least one polymerblock (A) among the aforementioned polymer blocks (A) which the blockcopolymer has is preferably 3,000 to 60,000, and more preferably 4,000to 50,000. When the block copolymer has at least one polymer block (A)having a weight average molecular weight falling within theaforementioned range, the mechanical strength is more improved, and thefilm moldability is excellent, too.

The “weight average molecular weight” described in this specificationand the claims is everywhere a weight average molecular weight expressedin terms of standard polystyrene as determined through the gelpermeation chromatography (GPC). The weight average molecular weight ofeach of the polymer blocks (A) which the block copolymer has can bedetermined by measuring the liquid sampled every time after thepolymerization to give each polymer block in the production process. Inaddition, for example, in the case of a triblock copolymer having astructure of A1-B-A2, the weight average molecular weights of the firstpolymer block A1 and the polymer block B are measured by theaforementioned method, and by subtracting these from the weight averagemolecular weight of the block copolymer, the weight average molecularweight of the second polymer block A2 can be determined. In addition, asanother method, in the case of the triblock copolymer having a structureof A1-B-A2, the weight average molecular weight of the total of thepolymer block (A) can be calculated from the weight average molecularweight of the block copolymer and the total content of the polymer block(A) as confirmed through the ¹H-NMR measurement, in which the weightaverage molecular weight of the deactivated first polymer block A1 iscalculated through the GPC measurement, and by subtracting it, theweight average molecular weight of the second polymer block A2 can beobtained, too.

The hydrogenated block copolymer of the present invention is satisfiedwith the following requirement (1).

<Requirement (1)>

The content of the polymer block (A) in the aforementioned blockcopolymer (in the case where the block of the hydrogenated copolymer hasplural polymer blocks (A), the total content thereof) is 1 to 30% bymass.

When the content of the polymer block (A) is less than 1% by mass, itbecomes difficult to form pellets of the hydrogenated block copolymer.On the other hand, when the content of the polymer block (A) is morethan 30% by mass, the flexibility becomes poor, the peak top intensityof tan δ is lowered, and the low shrinking properties and themoldability become poor. From the same viewpoint, the content of theaforementioned polymer block (A) is preferably 2 to 27% by mass, morepreferably 2 to 18% by mass, still more preferably 3 to 18% by mass,especially preferably 3.5 to 18% by mass, and most preferably 3.5 to 15%by mass. In addition, taking into consideration the matter that it iseasy to form a microphase-separated structure of a sphere as mentionedlater, the content of the polymer block (A) is preferably 3 to 15% bymass, more preferably 3.5 to 11% by mass, and still more preferably 3.5to 4.5% by mass. Taking into consideration the handling properties andthe mechanical physical properties of the film, the content of thepolymer block (A) is preferably 6 to 18% by mass, more preferably 6 to15% by mass, still more preferably 8 to 15% by mass, and especiallypreferably 10 to 15% by mass.

The content of the polymer block (A) in the block copolymer is a valuedetermined through the ¹H-NMR measurement, and in more detail, it is avalue measured according to the method described in the section ofExamples.

(Polymer Block (B))

The polymer block (B) contains a structural unit derived from at leastone selected from the group consisting of a conjugated diene compoundand isobutylene in an amount of 30 mol % or more, preferably 50 mol % ormore, more preferably 65 mol % or more, and still more preferably 80 mol% or more.

The polymer block (B) may contain 30 mol % or more of a structural unitderived from a conjugated diene compound, may contain 30 mol % or moreof a structural unit derived from isobutylene, or may contain 30 mol %or more of a structural unit derived from a mixture of a conjugateddiene compound and isobutylene. In addition, the polymer block (B) maycontain 30 mol % or more of a structural unit derived from oneconjugated diene compound or may contain 30 mol % or more of astructural unit derived from two or more conjugated diene compounds.

Examples of the aforementioned conjugated diene compound includeisoprene, butadiene, hexadiene, 2,3-dimethyl-1,3-butadiene,1,3-pentadiene, and myrcene. Above all, isoprene, butadiene, and amixture of isoprene and butadiene are preferred, with isoprene beingmore preferred. In the case of a mixture of butadiene and isoprene,though a mixing ratio thereof [isoprene/butadiene] (mass ratio) is notparticularly limited, it is preferably 5/95 to 95/5, more preferably10/90 to 90/10, still more preferably 40/60 to 70/30, and especiallypreferably 45/55 to 65/35. When the foregoing mixing ratio[isoprene/butadiene] is expressed in terms of a molar ratio, it ispreferably 5/95 to 95/5, more preferably 10/90 to 90/10, still morepreferably 40/60 to 70/30, and especially preferably 45/55 to 55/45.

As mentioned above, it is preferred that the polymer block (B) contains30 mol % or more of a structural unit derived from a conjugated dienecompound; it is also preferred that the polymer block (B) contains 30mol % or more of a structural unit derived from isoprene (hereinaftersometimes abbreviated as “isoprene unit”); it is also preferred that thepolymer block (B) contains 30 mol % or more of a structural unit derivedfrom butadiene (hereinafter sometime abbreviated as “butadiene unit”);and it is also preferred that the polymer block (B) contains 30 mol % ormore of a structural unit derived from a mixture of isoprene andbutadiene (hereinafter sometimes abbreviated as “mixture unit ofisoprene and butadiene”).

In the case where the polymer block (B) has two or more structuralunits, the bonding mode thereof can be random, tapered, completelyalternate, partially block, or block, or may be in the form of acombination of two or more thereof.

<Requirement (2)>

(Average Value of Methylene Chain Length of Polymer Block (B)>

In the present invention, when the polymer block (B) is regarded ashaving a structure with a hydrogenation rate of 100 mol %, an averagevalue of a methylene chain length (hereinafter sometimes referred to as“average methylene chain length”) of a main chain of the structural unitderived from at least one selected from the group consisting of aconjugated diene compound and isobutylene is 1.0 to 6.0. Here, themethylene chain length expresses to what extent the methylene grouprepresented by —CH₂— continuously bonds.

When the average methylene chain length is more than 6.0,crystallization is liable to occur, the damping properties are lowered,and when used for a laminated glass, the sound insulation properties arelowered. From the same viewpoint, the average methylene chain length ispreferably 1.0 to 5.0, more preferably 1.0 to 4.0, still more preferably1.0 to 3.5, yet still more preferably 1.5 to 3.5, especially preferably1.5 to 3.0, and most preferably 1.5 to 2.2.

The average methylene chain length is hereunder described whileexpressing the structures.

<Requirement (3)>(Average Value of Substituent Constant (ν) of Side Chain which MainChain has Per Ethylene Unit in Polymer Block (B)>

In the present invention, it is preferred that when the polymer block(B) is regarded as having a structure with a hydrogenation rate of 100mol %, an average value of a substituent constant (ν) (hereinaftersometimes referred to “average substituent constant”) of a side chainwhich the main chain has per ethylene unit is 0.25 to 1.1. Here, theaverage substituent constant of a side chain which the main chain hasper ethylene unit expresses an average value of bulkiness of thesubstituent serving as a side chain, and with respect to the substituentconstant (ν), “Journal of the American Chemical Society” (1975), Vol.97, pp. 1552-1556 can be made by reference. When the average substituentconstant is 0.25 or more, not only the damping properties become high,but also when used for a laminate (for example, a laminated glass), thesound insulation properties become high, and when it is 1.1 or less, thegeneration of rigidity of the main chain can be suppressed, the dampingproperties become high, and when used for a laminate (for example, alaminated glass), the sound insulation properties become high. From thesame viewpoint, the average substituent constant is more preferably 0.30to 0.55, still more preferably 0.33 to 0.55, and especially preferably0.33 to 0.50.

With respect to the substituent constant (ν), though specific examplesthereof are shown in the following Table 1, besides, values described in“Journal of the American Chemical Society” (1975), Vol. 97, pp.1552-1556 and “Journal of Organic Chemistry” (1976), Vol. 41, pp.2217-2220 can be utilized.

TABLE 1 Substituent of side chain Substituent constant (v) H 0 Methylgroup 0.52 t-Butyl group 1.24 Ethyl group 0.56 n-Propyl group 0.68Isopropyl group 0.76 n-Butyl group 0.68 s-Butyl group 1.02 Phenyl group0.57

The average substituent constant is determined by calculating an averagevalue of the substituent constant (ν) of each side chain. For example,in the case where the aforementioned conjugated diene compound isisoprene, and the content ratio of the 1,4-bond unit and the 3,4-bondunit is 40/60 (molar ratio), the average substituent constant is 0.47and can be determined as follows.

In addition, in the case where the aforementioned conjugated dienecompound is butadiene, and the content ratio of the 1,4-bond unit andthe 1,2-bond unit is 23/77 (molar ratio), the average substituentconstant is 0.35 and can be determined as follows.

In addition, in the case where the aforementioned conjugated dienecompound is a mixture of isoprene and butadiene (molar ratio: 50/50),the content ratio of the 1,4-bond unit and the 3,4-bond unit in isopreneis 40/60 (molar ratio), and the content ratio of the 1,4-bond unit andthe 1,2-bond unit in butadiene is 40/60 (molar ratio), the averagesubstituent constant is 0.36 and can be determined as follows.

In addition, in the case where though the aforementioned conjugateddiene compound is mainly isoprene, it contains 12 mol % of styrene, andthe content ratio of the 1,4-bond unit and the 3,4-bond unit in isopreneis 40/60 (molar ratio), the average substituent constant is 0.48 and canbe determined as follows.

<Requirement (4)>(Vinyl Bond Amount of Polymer Block (B))

In the case where the constitutional unit constituting the polymer block(B) is any one of an isoprene unit, a butadiene unit, and a mixture unitof isoprene and butadiene, as the bonding mode of each of isoprene andbutadiene, in the case of butadiene, the 1,2-bond and the 1,4-bond canbe taken, and in the case of isoprene, the 1,2-bond, the 3,4-bond, andthe 1,4-bond can be taken. In the block copolymer, the total of thecontents of the 3,4-bond unit and the 1,2-bond unit (hereinaftersometimes referred to as “vinyl bond amount”) in the polymer block (B)is preferably 20 mol % or more, more preferably 40 mol % or more, andstill more preferably 50 mol % or more. In addition, though there is noparticular limitation, the vinyl bond amount in the polymer block (B) ispreferably 90 mol % or less, and more preferably 85 mol % or less. Here,the vinyl bond amount is a value calculated through the ¹H-NMRmeasurement according to the method described in the section ofExamples.

In the case where the polymer block (B) is composed only of butadiene,the aforementioned wording “contents of the 3,4-bond unit and the1,2-bond unit” is replaced with the wording “content of the 1,2-bondunit” and applied.

From the viewpoint of damping properties as well as sound insulationproperties when formed into a laminate (for example, a laminated glass)and so on, the weight average molecular weight of the total of theaforementioned polymer block (B) which the block copolymer has ispreferably 15,000 to 800,000, more preferably 50,000 to 700,000, stillmore preferably 70,000 to 600,000, especially preferably 90,000 to500,000, and most preferably 130,000 to 450,000 in the state before thehydrogenation.

The polymer block (B) may contain a structural unit derived from apolymerizable monomer other than the conjugated diene compound andisobutylene so long as the object and effects of the present inventionare not impaired. In this case, in the polymer block (B), the content ofthe structural unit derived from a polymerizable monomer other than theconjugated diene compound and isobutylene is preferably less than 70 mol%, more preferably less than 50 mol %, still more preferably less than35 mol %, and especially preferably less than 20 mol %. Though a lowerlimit value of the content of the structural unit derived from apolymerizable monomer other than the conjugated diene compound andisobutylene is not particularly limited, it may be 0 mol %, may be 5 mol%, and may be 10 mol %.

Preferred examples of the other polymerizable monomer include at leastone compound selected from the group consisting of aromatic vinylcompounds, such as styrene, α-methylstyrene, o-methylstyrene,m-methylstyrene, p-methylstyrene, p-t-butylstyrene, 2,4-dimethylstyrene,vinylnaphthalene, and vinylanthracene; as well as methyl methacrylate,methyl vinyl ether, N-vinylcarbazole, β-pinene, 8,9-p-menthene,dipentene, methylene norbornene, 2-methylenetetrahydrofuran,1,3-cyclopentadiene, 1,3-cyclohexadiene, 1,3-cycloheptadiene, and1,3-cyclooctadiene. Above all, styrene, α-methylstyrene, andp-methylstyrene are preferred, with styrene being more preferred.

In the case where the polymer block (B) contains a structural unitderived from a polymerizable monomer other than the conjugated dienecompound and isobutylene, a specific combination thereof is preferablyisoprene and styrene, or butadiene and styrene, and more preferablyisoprene and styrene.

In the case where the polymer block (B) contains a structural unitderived from a polymerizable monomer other than the conjugated dienecompound and isobutylene, the bonding mode thereof is not particularlylimited, and though it may be any of random and tapered ones, it ispreferably random one.

The block copolymer may contain at least one aforementioned polymerblock (B). In the case where the block copolymer has two or more polymerblocks (B), those polymer blocks (B) may be the same as or differentfrom each other.

(Bonding Mode of Polymer Block (A) and Polymer Block (B))

In the block copolymer, so long as the polymer block (A) and the polymerblock (B) bond to each other, the bonding mode thereof is notparticularly limited, and it may be any one of a linear bonding mode, abranched bonding mode, and a radial bonding mode, or a combination oftwo or more thereof. Above all, the bonding mode of the polymer block(A) and the polymer block (B) is preferably a linear bonding mode, andexamples thereof include, when the polymer block (A) is represented byA, and the polymer block (B) is by B, a diblock copolymer represented byA-B, a triblock copolymer represented by A-B-A or B-A-B, a tetrablockcopolymer represented by A-B-A-B, a pentablock copolymer represented byA-B-A-B-A or B-A-B-A-B, and an (A-B)nX type copolymer (wherein Xrepresents a coupling agent residue, and n represents an integer of 3 ormore). Above all, a linear triblock copolymer or diblock copolymer ispreferred, and an A-B-A type triblock copolymer is preferably used fromthe viewpoint of flexibility, easiness of production, and so on.

Here, in this specification, in the case where polymer blocks of thesame kind bond linearly via a bifunctional coupling agent or the like,all the bonding polymer blocks are dealt with as one polymer block.According to this, including the above-mentioned exemplifications, thepolymer block to be strictly expressed as Y-X-Y (wherein X represents acoupling residue) is expressed as Y as a whole except for the case whereit must be specifically differentiated from a single polymer block Y. Inthis description, the polymer block of this kind that contains acoupling agent residue is dealt with as above, and therefore, forexample, a block copolymer that contains a coupling agent residue and isto be strictly expressed as A-B-X-B-A (wherein X represents a couplingagent residue) is expressed as A-B-A and is dealt with as an example ofa triblock copolymer.

The present invention is concerned with a hydrogenation product of theaforementioned block copolymer (also referred to as “hydrogenated blockcopolymer”).

From the viewpoint of heat resistance, weather resistance, and dampingproperties as well as sound insulation when formed into a laminate (forexample, a laminated glass), the carbon-carbon double bond which thepolymer block (B) has is hydrogenated in a rate of preferably 80 mol %or more, more preferably 85 mol % or more, still more preferably 89 mol% or more, yet still more preferably 90 mol % or more, and especiallypreferably 93 mol % or more. The foregoing value is sometimes referredto as “hydrogenation rate”. Though an upper limit value of thehydrogenation rate is not particularly limited, the upper limit valuemay be 99 mol % and may be 98 mol %.

The aforementioned hydrogenation rate is a value obtained by determiningthe content of the carbon-carbon double bond in the structural unitderived from the conjugated diene compound in the polymer block (B)through the ¹H-NMR measurement after the hydrogenation, and in moredetail, it is a value according to the method described in the sectionof Examples.

(Weight Average Molecular Weight (Mw) of Hydrogenated Block Copolymer)

The weight average molecular weight (Mw) of the hydrogenated blockcopolymer as expressed in terms of standard polystyrene by means of thegel permeation chromatography is preferably 15,000 to 800,000, morepreferably 50,000 to 700,000, still more preferably 70,000 to 600,000,especially preferably 90,000 to 500,000, and most preferably 130,000 to450,000. When the weight average molecular weight of the block copolymeris 15,000 or more, the heat resistance becomes high, and when it is800,000 or less, the moldability becomes favorable.

So long as the object and effects of the present invention are notimpaired, the hydrogenated block copolymer of the present invention mayhave one or more functional groups, such as a carboxy group, a hydroxygroup, an acid anhydride group, an amino group, and an epoxy group, in amolecular chain and/or a molecular end, and it may also be one nothaving a functional group.

(Peak Top Intensity of Tan δ and Peak Top Temperature of Tan δ)

With respect to a test piece prepared by pressurizing the hydrogenatedblock copolymer of the present invention at a temperature of 230° C. anda pressure of 10 MPa for 3 minutes to prepare a single-layer sheethaving a thickness of 1.0 mm and cutting out the single-layer sheet in adisk shape, its peak top intensity of tan δ as measured under acondition at a strain amount of 0.1%, a frequency of 1 Hz, a measurementtemperature of −70 to 200° C., and a temperature rise rate of 3° C./minin conformity of JIS K7244-10 (2005) may be 0.5 or more. As for onehaving a higher peak top intensity of tan δ, the value may be 1.0 ormore, further 1.5 or more, and still further 2.0 or more. In view of thefact that the peak top intensity of tan δ is high, the hydrogenatedblock copolymer of the present invention is excellent in the dampingproperties and the sound insulation properties.

The peak top intensity of tan δ indicates a value of tan δ when the peakof tan δ is maximum. In more detail, the measurement method of the peaktop intensity of tan δ is one described in the section of Examples.

In the case where the hydrogenated block copolymer of the presentinvention is used for an intermediate film for laminated glass asmentioned later, the peak top temperature of tan δ as measured under theaforementioned conditions (temperature at which the peak of tan δbecomes maximum) is preferably −40 to 35° C., more preferably −25 to 15°C., and still more preferably −15 to 5° C. In addition, in the casewhere the hydrogenated block copolymer of the present invention is usedfor an application of sound insulator or vibration damping material asmentioned later, in particular, an application of sound insulator orvibration damping material of an automobile, the aforementioned peak toptemperature of tan δ is preferably −10 to 50° C., more preferably 0 to40° C., and still more preferably 10 to 35° C.

As a value of a storage modulus (G′) of the hydrogenated block copolymerat ((peak top temperature of tan δ)+30° C.) is lower, the energyabsorption on glass transition becomes larger, and therefore, thedamping properties become high, and the sound insulation propertiesbecome high when used for a laminate (for example, a laminated glass).The storage modulus (G′) at ((peak top temperature of tan δ)+30° C.) ispreferably 0.01 to 3 MPa, more preferably 0.03 to 1 MPa, still morepreferably 0.05 to 0.7 MPa, and especially preferably 0.1 to 0.5 MPa.

When a minimum value of a value obtained by differentiating the storagemodulus (G′) of the hydrogenated block copolymer with the temperature isdefined as “d(G′)/dTemp.”, as this value is smaller, the peak topintensity of tan δ of the hydrogenated block copolymer becomes higher,and the hydrogenated block copolymer is more excellent in the dampingproperties and the sound insulation properties. The d(G′)/dTemp. ispreferably −20 MPa/° C. or less, more preferably −30 MPa/° C. or less,still more preferably −40 MPa/° C. or less, and especially preferably−43 MPa/° C. or less.

(Morphology)

The morphology of a film having a thickness of 1 mm, which is obtainedby molding the hydrogenated block copolymer of the present inventionunder a pressurizing condition at a temperature of 230° C. and apressure of 10 MPa for 3 minutes, has a microphase-separated structureof a sphere as illustrated in FIG. 1 or a cylinder as illustrated inFIG. 2 . In the case where the morphology of the film has amicrophase-separated structure of a sphere, the polymer block (A)becomes spherical and exists in the polymer block (B), whereas in thecase where the morphology of the film has a microphase-separatedstructure of a cylinder, the polymer block (A) becomes cylindrical andexists in the polymer block (B). As mentioned above, as the content ofthe aforementioned polymer block (A) is smaller, the morphology of thefilm more likely has a microphase-separated structure of a sphere.

In view of the fact that the morphology of the film obtained throughmolding as mentioned above has a microphase-separated structure of asphere or cylinder, the damping properties and the sound insulatingproperties when formed into a laminate (for example, a laminated glass)become much more higher. From the same viewpoint, it is more preferredthat the morphology of the film has a microphase-separated structure ofa sphere.

As illustrated in FIG. 3 , in the case where the film has amicrophase-separated structure of a lamella structure where a layer ofthe polymer block (A) and a layer of the polymer block (B) arealternately superimposed, the film is poor in the moldability, thedamping properties, and the sound insulation properties when formed intoa laminate (for example, a laminated glass).

(Shrinkage Factor in MD Direction)

In the hydrogenated block copolymer of the present invention, withrespect to the shrinkage factor in the MD direction (machine direction)as defined below, it is possible to achieve 20% or less, and it is alsopossible to achieve 15% or less. It may be said that the matter that theshrinkage factor is 15% or less is excellent in the low shrinkingproperties.

Shrinkage factor in the MD direction: after stationarily placing aribbon sheet (MD/TD=4.0 cm/3.5 cm, thickness=1 mm) obtained by extrusionmolding under an unstretched condition at 230° C. on talc at 230° C. forone week, when the length in the MD direction is taken as y, and aninitial length (4.0 cm) in the MD direction is taken as x, the shrinkagefactor in the MD direction is defined as {(x−y)/x}×100(%).

The shrinkage factor can be 10% or less, and it may be further 6% orless and 3% or less. TD means the transverse direction.

(Production Method of Hydrogenated Block Copolymer)

The hydrogenated block copolymer of the present invention can beproduced according to a solution polymerization method, an emulsionpolymerization method, a solid-phase polymerization method, or the like.Above all, a solution polymerization method is preferred, and forexample, a known method, such as an ionic polymerization method, e.g.,anionic polymerization and cationic polymerization, or a radicalpolymerization method, is applicable. Above all, an anionicpolymerization method is preferred. In the anionic polymerizationmethod, an aromatic vinyl compound and at least one selected from thegroup consisting of a conjugated diene compound and isobutylene aresuccessively added in the presence of a solvent, an anionicpolymerization initiator, and optionally, a Lewis base, to obtain ablock copolymer, and optionally, a coupling agent is added to allow themixture to react with other, followed by subjecting the block copolymerto hydrogenation, whereby the hydrogenated block copolymer can beobtained.

In the aforementioned method, examples of an organic lithium compoundwhich may be used as the polymerization initiator for anionicpolymerization include methyllithium, ethyllithium, n-butyllithium,sec-butyllithium, tert-butyllithium, and pentyllithium. Examples of adilithium compound which may also be used as the polymerizationinitiator include naphthalenedilithium and dilithiohexylbenzene.

Examples of the aforementioned coupling agent include dichloromethane,dibromomethane, dichloroethane, dibromoethane, dibromobenzene, andphenyl benzoate.

The amount of each of the polymerization initiator and the couplingagent to be used is suitably determined depending on the desired weightaverage molecular weight of the intended hydrogenated block copolymer.In general, the initiator, such as an alkyllithium compound and adilithium compound, is used preferably in a proportion of 0.01 to 0.2parts by mass based on 100 parts by mass of the total amount of themonomers to be used for the polymerization, inclusive of an aromaticvinyl compound, butadiene, and isoprene. In the case where the couplingagent is used, the amount thereof to be used is preferably 0.001 to 0.8parts by mass based on 100 parts by mass of the total amount of themonomers.

The solvent is not particularly limited so long as it does not adverselyaffect the anionic polymerization reaction. Examples thereof includealiphatic hydrocarbons, such as cyclohexane, methylcyclohexane,n-hexane, and n-pentane; and aromatic hydrocarbons, such as benzene,toluene, and xylene. The polymerization reaction is typically performedat a temperature of 0 to 100° C., and preferably 10 to 70° C. for 0.5 to50 hours, and preferably 1 to 30 hours.

In the case where the polymer block (B) of the block copolymer is astructural unit derived from a conjugated diene, the content of each ofthe 3,4-bond and the 1,2-bond of the polymer block (B) can be increasedby a method of adding a Lewis base as a co-catalyst on thepolymerization.

Examples of the Lewis base which can be used include ethers, such asdimethyl ether, diethyl ether, and tetrahydrofuran; glycol ethers, suchas ethylene glycol dimethyl ether and diethylene glycol dimethyl ether;and amines, such as triethylamine, N,N,N′,N′-tetramethylenediamine, andN-methylmorpholine. These Lewis bases can be used either alone or incombination of two or more thereof.

In the case where the aforementioned polymer block (B) contains astructural unit derived from a conjugated diene compound, in particular,isoprene and/or butadiene, the addition amount of the Lewis base isdetermined depending upon the intended vinyl bonding amount of theisoprene unit and/or the butadiene unit constituting the polymer block(B). For that reason, though the addition amount of the Lewis base isnot strictly limited, it is preferred to use the Lewis base in an amountin the range of typically from 0.1 to 1,000 mol, and preferably from 1to 100 mol per gram atom of lithium contained in the alkyllithiumcompound or the dilithium compound to be used as the polymerizationinitiator.

After performing the polymerization according to the aforementionedmethod, an active hydrogen compound, such as an alcohol, a carboxylicacid, and water, is added to stop the polymerization reaction.Thereafter, a hydrogenation reaction is performed in an inert organicsolvent in the presence of a hydrogenation catalyst. The hydrogenationreaction can be carried out under a hydrogen pressure of 0.1 to 20 MPa,preferably 0.5 to 15 MPa, and more preferably 0.5 to 5 MPa at a reactiontemperature of 20 to 250° C., preferably 50 to 180° C., and morepreferably 70 to 180° C. for a reaction time of typically 0.1 to 100hours, and preferably 1 to 50 hours.

Examples of the hydrogenation catalyst include Raney nickel; aheterogeneous catalyst having a metal, such as Pt, Pd, Ru, Rh, and Ni,supported on an elemental substance, such as carbon, alumina, anddiatomaceous earth; a Ziegler-based catalyst composed of a combinationof a transition metal compound with an alkylaluminum compound, analkyllithium compound, or the like; and a metallocene-based catalyst.

The hydrogenated block copolymer thus obtained can be acquired bysolidification by pouring the polymerization reaction liquid intomethanol or the like, followed by heating or drying under reducedpressure; or subjecting to so-called steam stripping by pouring thepolymerization reaction liquid into hot water along with steam andsubjecting the solvent to azeotropic removal, followed by heating ordrying under reduced pressure.

[Use]

The hydrogenated block copolymer of the present invention is excellentin the damping properties and the sound insulating properties whenformed into a laminate (for example, a laminated glass). For thatreason, the present invention also provides an intermediate film forlaminated glass containing the hydrogenated block copolymer of thepresent invention. In addition, the present invention provides a damrubber, a shoe sole material, a flooring material, and so on, eachcontaining the hydrogenated block copolymer of the present invention.Furthermore, the hydrogenated block copolymer of the present inventionis useful as a sound insulator and a vibration damping material. Thehydrogenated block copolymer of the present invention may also be usedfor a weather strip, a floor mat, and so on.

In particular, when the hydrogenated block copolymer of the presentinvention is used as an intermediate film for laminated glass, theintermediate film is excellent in the low shrinking properties, andtherefore, it is possible to provide an adhesive layer between theintermediate film and a glass.

In addition, the hydrogenated block copolymer of the present inventioncan be utilized for a sealing material, an adhesive, apressure-sensitive adhesive, a packing material, an O-ring, a belt, asoundproof material, and so on in various recorders in the field ofhousehold electrical appliance, such as a Blu-ray recorder and an HDDrecorder; and in various electrical products, such as a projector, agame player, a digital camera, a home video recorder, an antenna, aspeaker, an electronic dictionary, an IC recorder, a fax machine, acopying machine, a telephone, an intercom, a rice cooker, a microwaveoven, a multifunction microwave oven, a refrigerator, a dishwasher, adish dryer, an IH cooking heater, a hot plate, a vacuum cleaner, awashing machine, a battery charger, a sewing machine, an iron, a drier,a power-assisted bicycle, an air cleaner, a water purifier, an electrictoothbrush, lighting equipment, an air conditioner, an outdoor unit ofair conditioner, a dehumidifier, and a humidifier.

[Laminate]

The present invention also provides a laminate including an X layercontaining the hydrogenated block copolymer of the present invention anda Y layer laminated on at least one surface of the X layer. The laminateof the present invention is excellent in the damping properties and thesound insulation properties.

The laminate may be a laminate configured of one X layer and one Ylayer; may be a laminate configured of one X layer and two or more Ylayers; may be a laminate configured of two or more X layers and one Ylayer; or may be a laminate configured of two or more X layers and twoor more Y layers.

As for the configuration of the laminate of the present invention, whenthe X layer is expressed as “X”, and the Y layer is expressed as “Y”,though the configuration is not particularly limited, examples thereofinclude Y/X/Y, Y/X, and Y/X/Y/X/Y.

The plural Y layers may be made of the same material or may be made of adifferent material from each other. In the case where the plural Ylayers are made of a different material from each other, when the Ylayers made of a different material from each other are expressed in theorder of “Y1”, “Y2”, “Y3”, . . . , though the configuration of thelaminate of the present invention is not particularly limited, examplesthereof include Y1/X/Y1, Y2/Y1/X/Y1/Y2, Y1/X/Y2, X/Y1/Y2, Y1/X/Y2/Y3,and Y1/X/Y2/X/Y3. Above all, a laminate having a configuration ofY1/X/Y1, Y2/Y1/X/Y1/Y2, or Y1/X/Y2 is preferred, and a laminate having aconfiguration of Y1/X/Y1 or Y2/Y1/X/Y1/Y2 is more preferred.

Above all, a laminate including the X layer and a plurality of the Ylayers, in which the X layer is laminated between at least two Y layersand which is satisfied with the following formula (I), is preferred. Thevalue of the center of the formula (I), namely “(peak top frequency oftan δ)×(B/m)^(0.5)” is hereinafter sometimes referred to as “I value”.

As a result of various investigations made by the present inventors, ithas been found that B, m, and the peak top frequency of tan δ correlatewith the sound insulation properties, and the formula (I) expresses arelation thereof. The laminate which is satisfied with the formula (I)is preferred from the standpoint that a lowering of the sound insulationproperties due to a lowering of STL to be caused due to the coincidenceeffect can be effectively suppressed because the peak top frequency oftan δ of the hydrogenated copolymer becomes a value close to thecoincidence critical frequency of the laminate.200≤(peak top frequency of tan δ)×√{square root over(B/m)}≤2,000,000  (I)

In the formula (I), B represents a bending stiffness (Pa·m³) per unitwidth of the laminate; m represents a surface density (kg/m²) of thelaminate; and the peak top frequency (Hz) of tan δ represents afrequency when a peak of tan δ of the hydrogenated block copolymerdetermined according to the following method becomes maximum.

(Measurement Method of Peak Top Frequency of Tan δ)

With respect to a test piece having a thickness of 1.0 mm as prepared bypressurizing the hydrogenated block polymer at a temperature of 230° C.under a pressure of 10 MPa for 3 minutes, a master curve calculated bythe WLF method (Williams-Landel-Ferry method) is prepared on the basisof measured values as measured under a condition at a strain amount of0.1%, a frequency of 1 to 100 Hz, and a measurement temperature of 20°C., 10° C., 0° C., −10° C., and −30° C., respectively in conformity ofJIS K7244-10 (2005), and the peak top frequency of the hydrogenatedblock copolymer is calculated.

As for the measurement method of the bending stiffness per unit width asrepresented by B and the determination of the surface density asrepresented by m in the aforementioned formula (I), the followingmethods can be adopted.

(Measurement Method of Bending Stiffness (B) Per Unit Width)

A central portion of the laminate is fixed to a tip portion of anexciting force detector built in an impedance head of an exciter (poweramplifier/model 371-A) of a mechanical impedance instrument(manufactured by Ono Sokki Co., Ltd., mass cancel amplifier: MA-5500,channel data station: DS-2100). A vibration is given to the centralportion of the laminate at a frequency in the range of from 0 to 8,000Hz. An exciting force and an acceleration waveform at this point aredetected, thereby performing a damping test of the laminate by thecentral exciting method. A mechanical impedance at an exciting point(the central portion of the laminate to which a vibration has beengiven) is determined on the basis of the obtained exciting force and aspeed signal obtained by integrating an acceleration signal; and in animpedance curve obtained by setting the frequency on the abscissa andthe mechanical impedance on the ordinate, respectively, the bendingstiffness (Pa·m³) per unit width of the laminate is calculated from thefrequency expressing the peak (see ISO 16940:2008).

$B_{{eq},i} = {m_{s}\left( {f_{{res},i}\frac{2\pi L^{2}}{\lambda_{i}^{2}}} \right)}^{2}$

In the aforementioned formula, B_(eq) is a bending stiffness per unitwidth; ms is a surface density; f_(res) is a peak frequency of theimpedance test; L is a measured length of the laminated glass; and λ isa constant (=7.85476).

(Determination of Surface Density (m))

A mass per unit area of the laminate, namely a surface density can bedetermined by measuring a mass of the laminate and dividing it by asurface area. The surface area of the laminate can be determined from(length)×(breadth) upon making the laminate rectangular or square.

When the aforementioned formula (I) is satisfied, the sound insulationproperties become very high. From the same viewpoint, a lower limitvalue of the I value is preferably 400, more preferably 1,000, stillmore preferably 2,000, and especially preferably 4,000. In addition,from the same viewpoint, an upper limit value of the I value ispreferably 1,000,000, more preferably 400,000, still more preferably200,000, and especially preferably 100,000. These lower limit value andupper limit value can be adopted for the formula (I) independently or inan arbitrary combination.

[X Layer]

The X layer is a layer containing the hydrogenated block copolymer ofthe present invention, and it may be a layer composed only of thehydrogenated block copolymer of the present invention or may be a layercomposed of a composition containing a component other than thehydrogenated block copolymer of the present invention.

For example, even in the case where the X layer is used as anintermediate film for laminated glass, the X layer is a layer containingthe hydrogenated block copolymer of the present invention, and it may bea layer composed only of the hydrogenated block copolymer of the presentinvention or may be a layer composed of a composition containing acomponent other than the hydrogenated block copolymer of the presentinvention. In the case where the X layer is used as an intermediate filmfor laminated glass, examples of the component other than thehydrogenated block copolymer of the present invention include anantioxidant, a UV absorbent, a light stabilizer, a heat insulatingmaterial, and an antiblocking agent, but the component is notparticularly limited thereto. These materials can be used either aloneor in combination of two or more thereof.

Examples of the antioxidant include a phenol-based antioxidant, aphosphorus-based antioxidant, and a sulfur-based antioxidant.

As the UV absorber, in addition to a benzotriazole-based UV absorber, ahindered amine-based UV absorber, and a benzoate-based UV absorber, atriazine-based compound, a benzophenone-based compound, a malonic acidester compound, an oxalic acid anilide compound, and the like can beused.

Examples of the light stabilizer include a hindered amine-based lightstabilizer.

Examples of the heat insulating material include materials containing aheat ray shielding particle having a heat ray shielding function, or anorganic dye compound having a heat ray shielding function, in a resin ora glass. Examples of the particle having a heat ray shielding functioninclude a particle of an oxide, such as tin-doped indium oxide,antimony-doped tin oxide, aluminum-doped zinc oxide, tin-doped zincoxide, and silicon-doped zinc oxide; and a particle of an inorganicmaterial having a heat ray shielding functional, such as an LaB₆(lanthanum hexafluoride) particle. In addition, examples of the organicdye compound having a heat ray shielding function include adiimonium-based dye, an aminium-based dye, a phthalocyanine-based dye,an anthraquinone-based dye, a polymethine-based dye, a benzenedithiol-type ammonium-based compound, a thiourea derivative, and a thiolmetal complex.

Examples of the antiblocking agent include an inorganic particle and anorganic particle. Examples of the inorganic particle include particlesof oxides, hydroxides, sulfides, nitrides, halides, carbonates,sulfates, acetates, phosphates, phosphites, organic carboxylic acidsalts, silicic acid salts, titanic acid salts, and boric acid salts ofan element belonging to the Group IA, Group IIA, Group IVA, Group VIA,Group VIIA, Group VIIIA, Group IB, Group IIB, Group IIIB, or Group IVB,as well as hydrates thereof, and composite compounds and naturalminerals centering them. Examples of the organic particle include afluorine resin, a melamine-based resin, a styrene-divinylbenzenecopolymer, an acrylic resin silicone, and crosslinked products thereof.

For example, even in the case where the X layer is used for a soundinsulator or vibration damping material use, in particular, a soundinsulator or vibration damping material use of automobile, the X layeris a layer containing the hydrogenated block copolymer of the presentinvention, and it may be a layer composed only of the hydrogenated blockcopolymer of the present invention or may be a layer composed of acomposition containing a component other than the hydrogenated blockcopolymer of the present invention. In the case where the X layer isused for a sound insulator or vibration damping material use, inparticular, a sound insulator or vibration damping material use ofautomobile, examples of the component other than the hydrogenated blockcopolymer of the present invention include an antioxidant, a UVabsorbent, a light stabilizer, a heat insulating material, anantiblocking agent, a pigment, a dye, a softening agent, a crosslinkingagent, a crosslinking aid, and a crosslinking promoter, but thecomponent is not particularly limited thereto. These materials can beused either alone or in combination of two or more thereof.

With respect to the antioxidant, the UV absorber, the light stabilizer,the heat insulating material, and the antiblocking agent, the samematerials as those described above in the case where the X layer is usedas an intermediate film for laminated glass are exemplified.

Examples of the pigment include an organic pigment and an inorganicpigment. Examples of the organic pigment include an azo-based pigment, aquinacridone-based pigment, and a phthalocyanine-based pigment. Examplesof the inorganic pigment include titanium oxide, zinc oxide, zincsulfide, carbon black, a lead-based pigment, a cadmium-based pigment, acobalt-based pigment, an iron-based pigment, a chromium-based pigment,ultramarine blue, and Prussian blue.

Examples of the dye include an azo-based dye, an anthraquinone-baseddye, a phthalocyanine-based dye, a quinacridone-based dye, aperylene-based dye, a dioxazine-based dye, an anthraquinone-based dye,an indolinone-based dye, an isoindolinone-based dye, aquinoneimine-based dye, a triphenylmethane-based dye, a thiazole-baseddye, a nitro-based dye, and a nitroso-based dye.

As the softening agent, known softening agents, such as ahydrocarbon-based oil, e.g., a paraffinic hydrocarbon-based oil, anaphthenic hydrocarbon-based oil, and an aromatic hydrocarbon-based oil;a vegetable oil, e.g., peanut oil and rosin; a phosphoric acid ester;low-molecular weight polyethylene glycol; liquid paraffin; andhydrocarbon-based synthetic oils, e.g., low-molecular weightpolyethylene, an ethylene-α-olefin copolymer oligomer, liquidpolybutene, liquid polyisoprene or a hydrogenation product thereof, andliquid polybutadiene or a hydrogenation product thereof, can be used.These may be used either alone or in combination of two or more thereof.

Examples of the crosslinking agent include a radical generator, sulfur,and a sulfur compound.

Examples of the radical generator include organic peroxides, such as adialkyl monoperoxide, e.g., dicumyl peroxide, di-t-butyl peroxide, andt-butylcumyl peroxide; a diperoxide, e.g.,2,5-dimethyl-2,5-di(t-butylperoxy)hexane,2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3,bis(t-butyldioxyisopropyl)benzene,1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, and n-butyl4,4-bis(t-butylperoxy)valerate; a diacyl peroxide, e.g., benzoylperoxide, p-chlorobenzoyl peroxide, and 2,4-dichlorobenzoyl peroxide; amonoacylalkyl peroxide, e.g., t-butylperoxy benzoate; a percarbonate,e.g., t-butylperoxyisopropyl carbonate; and a diacyl peroxide, e.g.,diacetyl peroxide and lauroyl peroxide. These may be used either aloneor in combination of two or more thereof. Above all,2,5-dimethyl-2,5-di(t-butylperoxy)hexane and dicumyl peroxide arepreferred from the viewpoint of reactivity.

Examples of the sulfur compound include sulfur monochloride and sulfurdichloride.

As the crosslinking agent, in addition, a phenol-based resin, such as analkylphenol resin and a brominated alkylphenol resin; or a combinationof p-quinone dioxime and lead dioxide, a combination ofp,p′-dibenzoylquinone dioxime and trilead tetroxide, or the like canalso be used.

As the crosslinking aid, known crosslinking aids can be used. Examplesthereof include polyfunctional monomers, such as trimethylolpropanetrimethacrylate, trimethylolpropane triacrylate, triallyl trimellitate,triallyl 1,2,4-benzenetricarboxylate, triallyl isocyanurate,1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate,1,10-decanediol dimethacrylate, polyethylene glycol dimethacrylate,ethylene glycol dimethacrylate, diethylene glycol dimethacrylate,triethylene glycol dimethacrylate, divinylbenzene, glyceroldimethacrylate, and 2-hydroxy-3-acryloyloxypropyl methacrylate; stannouschloride, ferric chloride, organic sulfonic acids, polychloroprene, andchlorosulfonated polyethylene. The crosslinking aid may be used eitheralone or in combination of two or more thereof.

Examples of the crosslinking promoter include thiazoles, such asN,N-diisopropyl-2-benzothiazole sulfenamide, 2-mercaptobenzothiazole,and 2-(4-morpholinodithio)benzothiazole; guanidines, such asdiphenylguanidine and triphenylguanidine; aldehyde-amine-based reactionproducts or aldehyde-ammonia-based reaction products, such as abutylaldehyde-aniline reaction product and ahexamethylenetetramine-acetaldehyde reaction product; imidazolines, suchas 2-mercaptoimidazoline; thioureas, such as thiocarbanilide,diethylurea, dibutylthiourea, trimethylthiourea, anddi-ortho-tolylthiourea; dibenzothiazyl disulfide; thiuram monosulfidesor thiuram polysulfides, such as tetramethylthiuram monosulfide,tetramethylthiuram disulfide, and pentamethylenethiuram tetrasulfide;thiocarbamates, such as zinc dimethyldithiocarbamate, zincethylphenyldithiocarbamate, sodium dimethyldithiocarbamate, seleniumdimethyldithiocarbamate, and tellurium diethyldithiocarbamate;xanthogenates, such as zinc dibutylxanthogenate; and zinc oxide. Thecrosslinking promoter may be used either alone or in combination of twoor more thereof.

The hydrogenated block copolymer of the present invention may be usedupon being mixed with an additive, such as a crystal nucleating agent; ahydrogenated resin, such as a hydrogenated chroman.indene resin, ahydrogenated rosin-based resin, a hydrogenated terpene resin, and analicyclic hydrogenated petroleum resin; a tackifier resin, such as analiphatic resin composed of an olefin or diolefin polymer; hydrogenatedpolyisoprene, hydrogenated polybutadiene, butyl rubber, polyisobutylene,polybutene, a polyolefin-based elastomer; or other polymer, specificallyan ethylene-propylene copolymer, an ethylene-butylene copolymer, apropylene-butylene copolymer, a polyolefin-based resin, an olefin-basedpolymer, a polyethylene-based resin, or the like, without beingparticularly limited with respect to its use, so long as the effects ofthe present invention are not impaired.

Here, examples of the olefin constituting the aforementionedpolyolefin-based resin include ethylene, propylene, 1-butene, 1-pentene,1-hexene, 1-octene, 4-methyl-1-pentene, and cyclohexene. The olefinconstituting the polyolefin-based resin may be used either alone or incombination of two or more thereof. In particular, examples of thepolypropylene-based resin that is one of the polyolefin-based resinsinclude homopolypropylene, a propylene-ethylene random copolymer, apropylene-ethylene block copolymer, a propylene-butene random copolymer,a propylene-ethylene-butene random copolymer, a propylene-pentene randomcopolymer, a propylene-hexene random copolymer, a propylene-octenerandom copolymer, a propylene-ethylene-pentene random copolymer, and apropylene-ethylene-hexene random copolymer. In addition, a modifiedpolypropylene-based resin obtained by graft copolymerizing such apolypropylene-based resin with a modifier, such as an unsaturatedmonocarboxylic acid, e.g., acrylic acid, methacrylic acid, and crotonicacid; an unsaturated dicarboxylic acid, e.g., maleic acid, citraconicacid, and itaconic acid; an ester, an amide, or an imide of theforegoing unsaturated monocarboxylic acid or unsaturated dicarboxylicacid; and an unsaturated dicarboxylic acid anhydride, e.g., maleicanhydride, citraconic anhydride, and itaconic anhydride can also beused.

The olefin-based polymer is at least one olefin-based polymer selectedfrom the group consisting of an ethylene-propylene-diene copolymer(EPDM) rubber, an ethylene-vinyl acetate copolymer (EVA), and apolyethylene-based resin.

Examples of the diene which can be used as a raw material of theethylene-propylene-diene copolymer rubber include chain non-conjugateddienes, such as 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene,6-methyl-1,6-heptadiene, and 7-methyl-1,6-octadiene; cyclicnon-conjugated dienes, such as cyclohexadiene, dichloropentadiene,methyltetrahydroindene, 5-vinylnorbornene, 5-ethylidene-2-norbornene,5-methyl-2-norbornene, 5-isopropylidene-2-norbornene, and6-chloromethyl-5-isopropenyl-2-norbornene; and trienes, such as2,3-diisopropylidene-5-norbornene,2-ethylidene-3-isopropylidene-5-norbornene,2-propenyl-2,2-norbornadiene, 1,3,7-octatriene, and 1,4,9-decatriene.

Examples of the polyethylene-based resin include homopolymers ofethylene, such as high-density polyethylene, medium-densitypolyethylene, and low-density polyethylene; and ethylene-basedcopolymers, such as an ethylene/butene-1 copolymer, an ethylene/hexenecopolymer, an ethylene/heptene copolymer, an ethylene/octene copolymer,an ethylene/4-methylpentene-1 copolymer, an ethylene/vinyl acetatecopolymer, an ethylene/acrylic acid copolymer, an ethylene/acrylic acidester copolymer, an ethylene/methacrylic acid copolymer, and anethylene/methacrylic acid ester copolymer.

The hydrogenated block copolymer of the present invention may be usedupon being mixed with other polymer than those mentioned above, withoutbeing particularly limited with respect to its use, so long as theeffects of the present invention are not impaired.

Examples of such other polymer include polyphenylene ether-based resins;polyamide-based resins, such as polyamide 6, polyamide 6.6, polyamide6.10, polyamide 11, polyamide 12, polyamide 6.12,polyhexamethylenediamine terephthalamide, polyhexamethylenediamineisophthalamide, and a xylene group-containing polyamide; polyester-basedresins, such as polyethylene terephthalate and polybutyleneterephthalate; acrylic resins, such as polymethyl acrylate andpolymethyl methacrylate; polyoxymethylene-based resins, such as apolyoxymethylene homopolymer and a polyoxymethylene copolymer;styrene-based resins, such as a styrene homopolymer, an α-methylstyrenehomopolymer, an acrylonitrile-styrene resin, and anacrylonitrile-butadiene-styrene resin; a polycarbonate resin; anethylene-propylene copolymer rubber (EPM); a styrene-butadiene copolymerrubber, a styrene-isoprene copolymer rubber, or a hydrogenation productthereof or a modified product thereof; a natural rubber; a syntheticisoprene rubber, a liquid polyisoprene rubber, and a hydrogenationproduct or modified product thereof; a chloroprene rubber; an acrylrubber; an acrylonitrile-butadiene rubber; an epichlorohydrin rubber; asilicone rubber; a fluorine rubber; a chlorosulfonated polyethylene; aurethane rubber; a polyurethane-based elastomer; a polyamide-basedelastomer; a styrene-based elastomer; a polyester-based elastomer; and asoft polyvinyl chloride resin.

Furthermore, the hydrogenated block copolymer of the present inventionmay be used upon being mixed with various additives, without beingparticularly limited with respect to its use. Examples of such anadditive include inorganic fillers, such as talc, clay, mica, calciumsilicate, glass, glass hollow sphere, glass fiber, calcium carbonate,magnesium carbonate, basic magnesium carbonate, aluminum hydroxide,magnesium hydroxide, calcium hydroxide, zinc borate, dawsonite, ammoniumpolyphosphate, calcium aluminate, hydrotalcite, silica, diatomaceousearth, alumina, titanium oxide, iron oxide, zinc oxide, magnesium oxide,tin oxide, antimony oxide, barium ferrite, strontium ferrite, carbonblack, graphite, carbon fiber, active carbon, carbon hollow sphere,calcium titanate, lead zirconate titanate, silicon carbide, and mica;organic fillers, such as wood flour and starch; organic pigments; and aninorganic hollow particle.

The inorganic hollow particle is not particularly limited so long as itis a hollow particle formed of an inorganic material, such as ceramics.As the inorganic hollow particle, at least one selected from a glassballoon, a silica balloon, a Shirasu-balloon, an alumina balloon, azirconia balloon, and a fly ash balloon is preferred. An averageparticle diameter of the inorganic hollow particle is suitably in therange of, for example, 30 to 150 μm. The average particle diameter ofthe inorganic hollow particle is a 50% weight average particle diameter(D50 value) in the cumulative size distribution of particle sizedetermined by the laser light scattering method.

The hydrogenated block copolymer of the present invention may be usedupon being mixed with a lubricant, an antistatic agent, a flameretardant, a foaming agent, a water repellent, a waterproof agent, anelectroconductivity imparting agent, a thermal conductivity impartingagent, an electromagnetic wave shieldability imparting agent, afluorescent brightener, or a antimicrobial agent, as the need arises.

Even in the case of a dam rubber, a shoe sole material, a flooringmaterial, or the like, a resin composition containing, together with thehydrogenated block copolymer of the present invention, other materialmay also be used. Known materials which are used for a dam rubber, ashoe sole material, or a flooring material can be contained withoutbeing particularly limited. For example, those containing anolefin-based polymer, a crosslinking agent, a crosslinking aid, acrosslinking promoter, a foaming agent, a foaming aid, a processing aid,a resin of every kind, an additive of every kind, or the like may beused.

The production method of the foregoing resin composition is notparticularly limited, and known methods can be adopted. For example, theresin composition can be produced by mixing the hydrogenated blockcopolymer of the present invention and other material by using a mixingmachine, such as a Henschel mixer, a V blender, a ribbon blender, atumbler blender, and a conical blender, or after thus mixed, theresultant mixture is melt-kneaded with a single-screw extruder, atwin-screw extruder, a kneader, or the like. In addition, in the case ofperforming foaming, for example, the foamed product can be obtained byperforming injection foam molding of the resin composition having afoaming agent dry-blended therein in a die provided with a cavity havinga desired shape.

In the case where the X layer is a layer composed of the compositioncontaining a component other than the hydrogenated block copolymer ofthe present invention, though the content of the hydrogenated blockcopolymer of the present invention in the composition is notparticularly limited, from the viewpoint of damping properties and soundinsulation properties, it is preferably 50% by mass or more, morepreferably 60% by mass or more, still more preferably 80% by mass ormore, especially preferably 90% by mass or more, and most preferably 95%by mass or more.

Though the thickness of the X layer is not particularly limited, it ispreferably 10 to 800 μm, more preferably 30 to 500 μm, still morepreferably 50 to 500 μm, and especially preferably 70 to 350 μm. Inparticular, the thickness of the X layer may be 50 to 150 m and may be200 to 350 μm.

[Y Layer]

In the laminate of the present invention, though there is no particularlimitation, the aforementioned Y layer or at least one of theaforementioned plural Y layers is preferably a glass layer. In thiscase, the X layer serves as an intermediate film for laminated glass.The thickness of the glass layer (in the case of the plural glass layer,the thickness means a thickness of one layer) is preferably 0.5 to 5 mm,more preferably 0.5 to 3.0 mm, still more preferably 1.0 to 2.5 mm, andespecially preferably 1.2 to 1.8 mm. When the thickness of the glasslayer is set to 5 mm or less from the viewpoint of weight reduction, thethickness of the glass layer becomes thinner than that of theconventional ones, and therefore, the sound insulation properties areoriginally liable to be lowered. However, so far as a laminate using thehydrogenated block copolymer of the present invention is concerned,sufficient sound insulation properties are revealed. When the thicknessof the glass layer is 0.5 mm or more, sufficient sound insulationproperties can be obtained.

The glass which is used for the glass layer is not particularly limited,and examples thereof include inorganic glasses, such as a float plateglass, a polished plate glass, a figured plate glass, a wirenet-reinforced plate glass, and a heat ray-absorbing plate glass, andknown organic glasses. The glass may be colorless, colored, transparent,translucent, and non-transparent.

In the laminate of the present invention, at least one of theaforementioned plural Y layers may be a layer containing a thermoplasticresin (i) (adhesive auxiliary layer or skin layer) different from thehydrogenated block copolymer of the present invention. In thethermoplastic resin (i), a shear storage modulus (G′) at a temperature25° C. as measured by performing the complex shear viscosity test undera condition at a frequency of 1 Hz in conformity with JIS K7244-10(2005) is preferably 10 MPa or more, more preferably 15 MPa or more,still more preferably 20 MPa or more, especially preferably 20 to 70MPa, and most preferably 35 to 55 MPa. In this case, the weatherresistance and the strength of the X layer can be reinforced, and theadhesiveness to the aforementioned glass layer can be regulated.

In the case where at least one of the aforementioned plural Y layers isa layer containing the aforementioned thermoplastic resin (i) (adhesiveauxiliary layer or skin layer), from the viewpoint of sound insulationproperties, the thickness of the aforementioned X layer is preferably10% or more, more preferably 20% or more, and still more preferably 60%or more of the thickness of the adhesive auxiliary layer, and though anupper limit value thereof is not particularly limited, it is preferably200% or less, more preferably 160% or less, and still more preferably130% or less.

The layer containing the thermoplastic resin (i) (adhesive auxiliarylayer or skin layer) may be one having an uneven shape on the surfacethereof.

Examples of the thermoplastic resin (i) include a polyvinyl acetalresin, an ionomer, an ethylene-vinyl acetate copolymer, a urethaneresin, and a polyamide resin. Above all, from the viewpoint ofadhesiveness and transparency, a polyvinyl acetal resin and an ionomerare preferred.

(Polyvinyl Acetal Resin)

The polyvinyl acetal resin is a resin having a repeating unitrepresented by the following formula.

In the aforementioned formula, n represents a number of kinds ofaldehydes used for the acetalization reaction; R₁, R₂, . . . , R_(n)each represent an alkyl residue of the aldehyde used for theacetalization reaction, or a hydrogen atom; k₍₁₎, k₍₂₎, . . . , k_((n))each represent a proportion (molar ratio) of the constituent unitexpressed by [ ]; l represents a proportion (molar ratio) of the vinylalcohol unit; and m represents a proportion (molar ratio) of the vinylacetate unit.

However, k₍₁₎+k₍₂₎+ . . . +k_((n))+l+m=1; and any one of k₍₁₎, k₍₂₎, . .. , k_((n)), l, and m may be zero.

The respective repeating units are not particularly limited by theaforementioned arrangement order, and they may be arranged in a randomform, may be arranged in a block form, or may be arranged in a taperedform.

The production method of the polyvinyl acetal resin is not particularlylimited, and known methods, for example, a method described in WO2012/026501 A, can be adopted.

As the polyvinyl acetal resin, polyvinyl acetal resins described in WO2012/026501 A can be used, and above all, polyvinyl butyral (PVB) ispreferred.

(Ionomer)

Though the ionomer is not particularly limited, examples thereof includeresins having a constitutional unit derived from ethylene and aconstitutional unit derived from an α,β-unsaturated carboxylic acid, inwhich at least a part of the α,β-unsaturated carboxylic acid isneutralized with a metal ion. Examples of the metal ion include a sodiumion. In the ethylene-α,β-unsaturated carboxylic acid copolymer servingas a base polymer, though a content proportion of the constitutionalunit of the α,β-unsaturated carboxylic acid is not particularly limited,it is preferably 2% by mass or more, and more preferably 5% by mass ormore. In addition, though the content proportion of the constitutionalunit of the α,β-unsaturated carboxylic acid is not particularly limited,it is preferably 30% by mass or less, and more preferably 20% by mass orless.

Examples of the α,β-unsaturated carboxylic acid constituting the ionomerinclude acrylic acid, methacrylic acid, maleic acid, monomethyl maleate,monoethyl maleate, and maleic anhydride, Above all, acrylic acid andmethacrylic acid are preferred.

In the present invention, from the viewpoint of easiness ofavailability, an ionomer of an ethylene-acrylic acid copolymer and anionomer of an ethylene-methacrylic acid copolymer are preferred, and asodium ionomer of an ethylene-acrylic acid copolymer and a sodiumionomer of an ethylene-methacrylic acid copolymer are more preferred.

In the case where the Y layer is a layer containing the aforementionedthermoplastic resin (i), it may be a layer containing only theaforementioned thermoplastic resin (i) or may be a layer composed of acomposition containing a component other than the aforementionedthermoplastic resin (i).

Examples of the component other than the thermoplastic resin (i) includean adhesive strength regulator, a plasticizer, an antioxidant, a UVabsorber, a light stabilizer, an antiblocking agent, a pigment, a dye,and a heat insulating material, but the component is not particularlylimited thereto. These materials can be used either alone or incombination of two or more thereof.

As the adhesive strength regulator, those disclosed in WO 03/033583 Acan also be used. Examples thereof include an alkali metal salt and analkaline earth metal salt, and more specifically, examples thereofinclude salts of potassium, sodium, magnesium, or the like. Examples ofthe aforementioned salt include salts of an organic acid, such as acarboxylic acid, e.g., octanoic acid, hexanoic acid, butyric acid,acetic acid, and formic acid; and an inorganic acid, such ashydrochloric acid and nitric acid.

Though the plasticizer is not particularly limited, a carboxylic acidester-based plasticizer, such as a monovalent carboxylic acidester-based plasticizer and a polyvalent carboxylic acid ester-basedplasticizer; a phosphoric acid ester-based plasticizer; an organicphosphorous acid ester-based plasticizer; a polymer plasticizer, such asa carboxylic acid polyester-based plasticizer, a carboxylic acidpolyester-based plasticizer, and a polyalkylene glycol-basedplasticizer; an ester compound of a hydroxycarboxylic acid and apolyhydric alcohol, such as castor oil; and a hydroxycarboxylic acidester-based plasticizer, such an ester compound of a hydroxycarboxylicacid and a monohydric alcohol can be used.

With respect to the antioxidant, the UV absorber, the light stabilizer,the antiblocking agent, the pigment, the dye, and the heat insulatingmaterial, the same description as that described above for the X layeris applicable.

In the case where the Y layer is a layer composed of a compositioncontaining the aforementioned thermoplastic resin (i), though thecontent of the aforementioned thermoplastic resin (i) in the compositionis not particularly limited, from the viewpoint of adhesiveness or thelike, it is preferably 50% by mass or more, more preferably 60% by massor more, still more preferably 80% by mass or more, especiallypreferably 90% by mass or more, and most preferably 95% by mass or more.

Examples of a more specific preferred embodiment of the laminate of thepresent invention include a laminate [Y2/Y1/X/Y1/Y2] in which the glasslayer, the layer containing the thermoplastic resin (i), the X layer,the layer containing the thermoplastic resin (i), and the glass layerare laminated in this order; and from the viewpoint of rigidity,examples of a more preferred embodiment include a laminate in which theglass layer, the layer containing the ionomer, the X layer, the layercontaining the ionomer, and the glass layer are laminated in this order.From the viewpoint of control of adhesion to the glass, examples of amore preferred embodiment include a laminate in which the glass layer,the layer containing PVB, the X layer, the layer containing PVB, and theglass layer are laminated in this order.

The production method of the laminate of the present invention is notparticularly limited, and examples thereof include a method of using avacuum laminator, a method of using a vacuum bag, a method of using avacuum ring, and a method of using a nip roll. For example, for theproduction of a laminate [Y1/X/Y1] of a three-layer configuration oflayers containing the layer containing the thermoplastic resin (i), theX layer, and the layer containing the thermoplastic resin (i), a niproll is preferably used. In addition, for example, in the case oflaminating the Y2 layer of a laminate [Y2/Y1/X/Y1/Y2] of a five-layerconfiguration in which the glass layer, the layer containing thethermoplastic resin (i), the X layer, the layer containing thethermoplastic resin (i), and the glass layer are laminated in thisorder, it is preferred to adopt a vacuum laminator.

The condition under which the nip rolling is performed is notparticularly limited, and the laminate can be produced by sandwiching amolded article obtained through co-extrusion at about 180 to 230° C.using an extruder between two rolls, such as a metal mirror surface rolland then taking up at a predetermined taking-up speed. In addition, inthe case of using a vacuum laminator, a hot plate temperature ispreferably 140 to 190° C., an evacuation time is preferably 6 to 20minutes, a pressing pressure is preferably 35 to 65 MPa, and a pressingtime is preferably 10 to 30 minutes.

Furthermore, when the laminated glass that is one embodiment of thepresent invention is specifically described, its production method isnot particularly limited, and it is possible to produce it by aconventionally known method. Examples thereof include a method of usinga vacuum laminator, a method of using a vacuum bag, a method of using avacuum ring, and a method of using a nip roll. In addition, a method inwhich after temporary contact bonding, the resultant is placed in anautoclave to achieve primary contact bonding can also be adopted.

In the case of using a vacuum laminator device, lamination can be, forexample, achieved under reduced pressure of 1×10⁻⁶ to 3×10⁻² MPa at 100to 200° C., and especially 130 to 170° C. The method of using a vacuumbag or a vacuum ring is described in, for example, European Patent No.1235683, and the lamination can be, for example, achieved under apressure of about 2×10⁻² MPa at 130 to 145° C.

In the case of using a nip roll, for example, there is exemplified amethod in which after performing first temporary contact bonding at atemperature of not higher than a flow beginning temperature of thematerials of the adhesive auxiliary layer, such as the ionomer and thepolyvinyl acetal resin, temporary contact bonding is further performedunder a condition close to the flow beginning temperature.

It is preferred to carry out the primary contact bonding by anautoclave, for example, under a pressure of about 1 to 15 MPa at 130 to155° C. for about 0.5 to 2 hours depending upon the thickness andconfiguration of the module.

In order to provide the intermediate film for laminated glass of thepresent invention in the interior of the laminated glass, a laminatedglass may be fabricated by gathering glasses having the Y layer appliedon the both surfaces of the X layer and laminating them.

As one of preferred uses of the laminate with excellent sound insulationproperties of the present invention, a laminated glass is exemplified asmentioned above. Though the foregoing laminated glass is notparticularly limited, it is effectively utilized for, for example, awindow shield for automobile, a side glass for automobile, a sunroof forautomobile, a rear glass for automobile, or a glass for head-up display.

EXAMPLES

The present invention is hereunder described in more detail by referenceto Examples, but it should be construed that the present invention is byno means limited by these Examples.

[Each of Components Used in Examples]

A production method of each of the components used in the Examples andComparative Examples is hereunder described.

[Production Example 1] Production of Hydrogenated Block Copolymer

A nitrogen-purged and dried pressure-resistant container was chargedwith 50 kg of, as a solvent, cyclohexane and 20 g of a cyclohexanesolution of, as an anionic polymerization initiator, sec-butyllithiumhaving a concentration of 10.5% by mass (substantial addition amount ofsec-butyllithium: 2.1 g) and further charged with 260 g of, as a Lewisbase, tetrahydrofuran.

After subjecting the inside of the pressure-resistant container totemperature rise to 50° C., 0.16 kg of styrene (1) was added andpolymerized for 1 hour, 7.8 kg of isoprene was subsequently added andpolymerized for 2 hours, and 0.16 kg of styrene (2) was further addedand polymerized for 1 hour, thereby obtaining a reaction liquidcontaining a polystyrene-polyisoprene-polystyrene triblock copolymer.

To the reaction liquid, a Ziegler-based hydrogenation catalyst formed ofnickel octylate and trimethylaluminum was added in a hydrogenatmosphere, and reaction was performed under a condition at a hydrogenpressure of 1 MPa and 80° C. for 5 hours. After standing the reactionliquid for cooling and pressure discharge, the aforementioned catalystwas removed by water washing, and the residue was dried in vacuo,thereby obtaining a hydrogenation product of thepolystyrene-polyisoprene-polystyrene triblock copolymer (hereinaftersometimes referred to as “TPE-1”).

Each of the raw materials and its use amount are summarized in Table2-1.

[Production Examples 2 to 11 and 13 to 16 and Comparative ProductionExamples 1 to 5] Production of Hydrogenated Block Copolymers

Hydrogenated block copolymers (TPE-2) to (TPE-11), (TPE-13) to (TPE-16),and (TPE-1′) to (TPE-5′) were produced in the same manner as inProduction Example 1, except that each of the components and its useamount were changed as described in Table 2-1 or Table 2-2.

[Production Example 12] Production of Styrene-Isobutylene-StyreneTriblock Copolymer

In a stirrer-equipped reactor, 800 mL of methylene chloride which hadbeen dehydrated and purified with Molecular Sieves 4 A and 1,200 mL ofmethylcyclohexane which had been similarly dehydrated and purified werecharged; 1.3 g (5.4 mmol) of 1,4-bis(1-chloro-1-methylethyl)benzene, 2.4g (23 mmol) of 2,6-dimethylpyridine, 0.84 g (10.6 mmol) of pyridine, and210 g of isobutylene were added, respectively; and 7.7 g (41 mmol) oftitanium tetrachloride was further added at −78° C., thereby startingpolymerization. After the polymerization at −78° C. under stirring for 3hours, 0.6 g (5.9 mmol) of 2,6-dimethylpyridine and 60 g of styrene wereadded, thereby further performing polymerization at the same temperatureunder stirring for 4 hours.

To the resulting reaction mixed liquid, 200 mL of methanol was added toterminate the polymerization reaction. The resulting mixed liquid waswashed with water and subsequently re-precipitated in a large amount ofmethanol, thereby obtaining a styrene-isobutylene-styrene triblockcopolymer (TPE-12).

TABLE 2-1 Production of hydrogenated block copolymer Production Example1 2 3 4 5 6 7 5 9 Hydrogenated block copolymer TPE-1 TPE-2 TPE-3 TPE-4TPE-5 TPE-6 TPE-7 TPE-8 TPE-9 Use Cyclohexane 50 50 50 50 50 50 50 50 50amount sec-Butyllithium 0.020 0.020 0.020 0.028 0.054 0.076 0.111 0.0820.130 (kg) (10.5% by mass cyclohexane solution) (A) Styrene (1) 0.160.16 0.16 0.38 0.75 0.50 1.00 0.50 1.70 Styrene (2) 0.16 0.16 0.16 0.380.75 1.50 1.00 1.50 1.70 (B) Isoprene 7.80 6.40 7.80 8.75 11.00 8.208.20 13.31 Butadiene 6.50 14.60 6.50 Styrene (3) 1.40 LewisTetrahydrofuran 0.26 0.26 0.17 0.27 0.28 0.31 0.11 0.29 baseN,N,N′,N′-Tetramethyl- 0.030 ethylenediamine The components of thepolymer block (B) were used as a mixture.

TABLE 2-2 Production of hydrogenated block copolymer: Production ExampleComparative Production Example 10 11 13 14 15 16 1 2 3 4 5 Hydrogenatedblock copolymer TPE-10 TPE-11 TPE-13 TPE-14 TPE-15 TPE-16 TPE-1′ TPE-2′TPE-3′ TPE-4′ TPE-5′ Use Cyclohexane 50 50 50 50 50 50 50 50 50 50 50 a-sec-Butyllithium 0.125 0.101 0.060 0.075 0.020 0.020 0.186 0.217 0.0750.020 0.020 mount (10.5% by mass (kg) cyclohexane solution) (A) Styrene(1) 1.70 1.70 0.67 1.00 0.32 0.16 2.50 2.50 1.00 0.02 1.34 Styrene (2)1.70 1.70 0.33 1.00 0.16 2.50 2.50 1.00 0.02 1.34 (B) Isoprene 11.0013.30 7.80 5.85 6.49 8.10 5.44 Butadiene 15.00 3.24 5.16 11.70 1.16Styrene (3) 2.30 0.67 7.24 1.95 9.34 Lewis Tetrahydrofuran 0.29 0.110.26 0.26 0.11 0.11 0.26 0.27 base N,N,N′,N′- 0.065 0.020 Tetramethyl-ethylenediamine The components of the polymer block (B) were used as amixture.

Examples 1 to 16 and Comparative Examples 1 to 5

With respect to the hydrogenated block copolymer obtained in each of theProduction Examples and Comparative Production Examples, variousphysical properties were evaluated according to measurement methods asmentioned later. The results are shown in Tables 3 and 4.

However, in Comparative Example 4, the moldability was low, so that atest sheet for evaluation of the various physical properties could notbe prepared. Thus, the evaluation of various physical properties couldnot be performed.

A laminate (intermediate film for laminated glass) using an ionomer forthe Y1 layer [Y1 layer/X layer/Y1 layer] was produced according to thefollowing method; furthermore, a laminate (laminated glass) using aglass for the Y2 layer [Y2 layer/Y1 layer/X layer/Y1 layer/Y2 layer] wasproduced; and the evaluation of physical properties were performedaccording to the following methods. The results are also shown in Tables3 and 4.

(1. Preparation of Intermediate Film for Laminated Glass)

The hydrogenated block copolymer for the X layer was introduced into aT-die (multi-manifold type: width=500 mm) at 205° C. by using a venttype single-screw extruder having a diameter of screw of 50 mm under acondition at a temperature of 210° C. and a discharge rate of 4 kg/hr,and the ionomer for the Y1 layer (SentryGlas (registered trademark)Interlayer, manufactured by Du Pont) was introduced into the foregoingT-die by using a vent type single-screw extruder having a diameter ofscrew of 65 mm under a condition at a temperature of 205° C. and adischarge rate of 24 kg/hr.

A molded article coextruded from the T-die was nipped by two metalmirror surface rolls, one of which was set to 50° C., with the otherbeing set to 60° C., and taken up at a taking-up speed of 1.2 m/min,thereby molding an intermediate film for laminated glass (760 μm)[laminate 1] having a three-layer configuration of Y1 layer/X layer/Y1layer (330 μm/100 μm/330 μm).

In addition, an intermediate film for laminated glass (760 μm) [laminate2] having a three-layer configuration of Y1 layer/X layer/Y1 layer (253μm/253 μm/253 μm) was molded in the same manner.

(2. Preparation of Laminated Glass)

The aforementioned intermediate film for laminated glass [laminate 1]was sandwiched by two sheets of commercially available clear glasses[FL2 (four-side beveling processed), 300 mm in length×25 mm in width×2.0mm in thickness, manufactured by Sanshiba Glass Co., Ltd.] and treatedwith a vacuum laminator (“1522N”, manufactured by Nisshinbo MechatronicsInc.) under a condition at a hot plate temperature of 165° C. for anevacuation time of 12 minutes at a pressing pressure of 50 kPa for apressing time of 17 minutes, thereby preparing a laminated glass[laminate 3] having a five-layer configuration of Y2 layer/Y1 layer/Xlayer/Y1 layer/Y2 layer.

In addition, the same operations were performed in the same manner,except for using the laminate 2 in place of the aforementioned laminate1, thereby by preparing a laminated glass [laminate 4] having afive-layer configuration of Y2 layer/Y1 layer/X layer/Y1 layer/Y2 layer.

<Physical Properties of Hydrogenated Block Copolymer>

(1) Content of Polymer Block (A)

The hydrogenated block copolymer was dissolved in CDCl₃ and subjected to¹H-NMR measurement [apparatus: “ADVANCE 400 Nano bay” (manufactured byBruker Corporation), measurement temperature: 50° C.], therebycalculating the content of the polymer block (A) from a peak intensityderived from styrene.

(2) Morphology

The hydrogenated block copolymer was pressurized at a temperature of230° C. and a pressure of 10 MPa for 3 minutes, thereby preparing a filmhaving a thickness of 1 mm. The film was cut in a desired size toprepare a test piece, which was then subjected to surface shaping with adiamond cutter at a surface shaping temperature of −110° C. A crosssection (1 μm in square) of the test piece was observed with a scanningprobe microscope (SPM) (manufactured by SII Nano Technology Inc.) at ameasurement temperature of 25° C., thereby evaluating the morphology. Inthe case where the test piece has a microphase-separated structure ofany one of a sphere (FIG. 1 ), a cylinder (FIG. 2 ), and a lamella (FIG.3 ), that is indicated in Tables 3 and 4.

(3) Weight Average Molecular Weight (Mw)

A weight average molecular weight (Mw) of the hydrogenated blockcopolymer as expressed in terms of polystyrene was determined by meansof the gel permeation chromatography (GPC) under the followingcondition.

(GPC Measurement Apparatus and Measurement Condition)

-   -   Apparatus: GPC apparatus “HLC-8020” (manufactured by Tosoh        Corporation)    -   Separation columns: “TSKgel GMHXL”, “G4000HXL”, and “G5000HXL”,        all of which are manufactured by Tosoh Corporation, were        connected in series with each other.    -   Eluent: Tetrahydrofuran    -   Eluent flow rate: 1.0 mL/min    -   Sample concentration: 5 mg/10 mL    -   Column temperature: 40° C.    -   Detector: Differential refractive index (RI) detector    -   Calibration curve: Prepared using standard polystyrene        (4) Hydrogenation Rate of Hydrogenated Block Copolymer

A hydrogenation rate was determined through the ¹H-NMR measurement.

-   -   Apparatus: Nuclear magnetic resonator “ADVANCE 400 Nano Bay”        (manufactured by Bruker Corporation)    -   Solvent: Deuterated chloroform        (5) Average Methylene Chain Length

An average methylene chain length was calculated from the monomerspecies as well as a total value of the contents of the 1,2-bond and the3,4-bond (vinyl bond amount) on the basis of the aforementioneddescription.

(6) Average Substituent Constant of Side Chain

An average substituent constant of side chain was calculated from themonomer species as well as a total value of the contents of the 1,2-bondand the 3,4-bond (vinyl bond amount) on the basis of the aforementioneddescription.

(7) Vinyl Bond Amount of Polymer Block (B)

The block copolymer prior to hydrogenation was dissolved in CDCl₃ andsubjected to ¹H-NMR measurement [apparatus: “ADVANCE 400 Nano bay”(manufactured by Bruker Corporation), measurement temperature: 50° C.].A vinyl bond amount (the total of the contents of the 3,4-bond unit andthe 1,2-bond unit) was calculated from a ratio of the total peak area ofthe structural unit derived from isoprene and/or butadiene to the peakarea corresponding to the 3,4-bond unit and the 1,2-bond unit in theisoprene structural unit, the 1,2-bond unit in the butadiene structuralunit, or the aforementioned respective bond units in the case of thestructural unit derived from a mixture of isoprene and butadiene.

(8-1) Peak Top Temperature and Peak Top Intensity of Tan δ, and StorageModulus (G′) at ((Peak Top Temperature of Tan δ)+30° C.)

For the following measurement, by pressurizing the hydrogenated blockcopolymer at a temperature of 230° C. and a pressure of 10 MPa for 3minutes, a single-layer sheet having a thickness of 1.0 mm was prepared.The single-layer sheet was cut out in a disk shape, to provide a testsheet.

For the measurement, a strain-controlled dynamic viscoelasticityapparatus having a diameter of disk of 8 mm, “ARES-G2” (manufactured byTA Instruments Japan Inc.) was used as a parallel-plate oscillatoryrheometer on the basis of JIS K7244-10 (2005).

A gap between two flat plates was completely filled with theaforementioned test sheet, an oscillation was given to theaforementioned test sheet at a strain amount of 0.1% and a frequency of1 Hz, and the temperature was raised from −70° C. to 200° C. at aconstant rate of 3° C./min. The temperature of each of theaforementioned test sheet and the disk was kept until the measuredvalues of shear loss modulus and shear storage modulus did not change,thereby determining a storage modulus (G′) of the hydrogenated blockcopolymer, a maximum value of peak intensity of tan δ (peak topintensity), and a temperature obtained from the maximum value (peak toptemperature). In addition, a storage modulus (G′) at ((peak toptemperature of tan δ)+30° C.) was determined.

(8-2) Minimum Value of d(G′)/dTemp.

The storage modulus (G′) measured in the above (8-1) was used to definea storage modulus G′(T) at a certain temperature (T) and a storagemodulus G′(T+dT) at a point at which the temperature war raised by aminute amount (dT); d(G′)/dTemp.=(G′(T+dT)−G′(T))/dT was calculated fromthe foregoing values; and a minimum value of d(G′)/dTemp. from T=−70° C.to T=200° C. was determined.

(9) Shrinkage Factor in MD Direction

After stationarily placing a ribbon sheet (MD/TD=4.0 cm/3.5 cm,thickness=1 mm) obtained by extrusion molding the hydrogenated blockcopolymer obtained in each of the Production Examples under anunstretched condition at 230° C. on talc at 230° C. for one week, whenthe length in the MD direction is taken as y, and an initial length (4.0cm) in the MD direction is taken as x, the shrinkage factor in the MDdirection was determined according to the formula: {(x−y)/x}×100(%).

(10) Shear Storage Modulus (G′) of Y Layer

By pressurizing the ionomer at a temperature of 230° C. and a pressureof 10 MPa for 3 minutes, a single-layer sheet having a thickness of 1.0mm was prepared. The single-layer sheet was cut out in a disk shape, toprovide a test sheet.

A strain-controlled dynamic viscoelasticity apparatus having a diameterof disk of 8 mm, “ARES-G2” (manufactured by TA Instruments Japan Inc.)was used as a parallel-plate oscillatory rheometer on the basis of JISK7244-10.

A gap between two flat plates was completely filled with theaforementioned test sheet, an oscillation was given to theaforementioned test sheet at a strain amount of 0.1% and a frequency of1 Hz, and the temperature was raised from −40° C. to 100° C. at aconstant rate of 3° C./min. The temperature of each of theaforementioned test sheet and the disk was kept until the measuredvalues of shear loss modulus and shear storage modulus did not change,thereby measuring a shear storage modulus (G′) of the Y layer.

<Determination of I Value>

[1] A peak top frequency of tan δ of the hydrogenated block copolymerand a bending stiffness per unit width and a surface density (kg/m²) ofthe laminate were measured according to the following measurementmethods, and an I value was then calculated from the measured values.[1-1] Peak Top Frequency of Tan δ of Hydrogenated Block Copolymer

By using a test piece (thickness: 1.0 mm) prepared in the same manner asin the measurement of the above “(8) Peak Top Temperature of Peak TopStrength of tan δ”, a master curve calculated by the WLF method wasprepared on the basis of measured values as measured at a strain amountof 0.1%, a frequency of 1 to 100 Hz, and a measurement temperature of20° C., 10° C., 0° C., −10° C., and −30° C., respectively in conformityof JIS K7244-10 (2005), and the peak top frequency of the hydrogenatedblock copolymer was calculated.

Furthermore, in the aforementioned method, the measurement was performedin the same manner, except for setting the measurement temperature to20° C. and setting the frequency to 1 to 1,000,000 Hz, thereby preparinggraphs each expressing a relation between the frequency and tan δ. Theprepared graphs are shown as (b) in FIGS. 4 to 23 .

[1-2] Bending Stiffness (B: Pa·m³) Per Unit Width of Laminate (LaminatedGlass)

A central portion of the laminate (laminated glass) 3 or 4 obtained ineach Example was fixed to a tip portion of an exciting force detectorbuilt in an impedance head of an exciter (power amplifier/model 371-A)of a mechanical impedance instrument (manufactured by Ono Sokki Co.,Ltd., mass cancel amplifier: MA-5500, channel data station: DS-2100). Avibration was given to the central portion of the aforementionedlaminate at a frequency in the range of from 0 to 8,000 Hz. An excitingforce and an acceleration waveform at this point were detected, therebyperforming a damping test of the laminate (laminated glass) 3 or 4 bythe central exciting method.

A mechanical impedance at an exciting point (the central portion of thelaminate to which a vibration had been given) was determined on thebasis of the obtained exciting force and a speed signal obtained byintegrating an acceleration signal; and in an impedance curve obtainedby setting the frequency on the abscissa and the mechanical impedance onthe ordinate, respectively, a bending stiffness (Pa·m³) per unit widthof the laminate (laminated glass) 3 or 4 was calculated from thefrequency expressing the peak.

[1-3] Surface Density (m: Kg/m²) of Laminate (Laminated Glass)

A mass of the laminate (laminated glass) 3 or 4 obtained in each Examplewas measured and divided by a surface area (length: 300×10⁻³ m, width:25×10⁻³ m), thereby determining a mass per unit area of the laminate(laminated glass) 3 or 4, namely a surface area.

[2] Sound Transmission Loss (STL) of Laminate (Laminated Glass)

A central portion of the laminate (laminated glass) 3 or 4 obtained ineach Example was fixed to a tip portion of an exciting force detectorbuilt in an impedance head of an exciter (power amplifier/model 371-A)of a mechanical impedance instrument (manufactured by Ono Sokki Co.,Ltd., mass cancel amplifier: MA-5500, channel data station: DS-2100). Avibration was given to the central portion of the aforementionedlaminate at a frequency in the range of from 0 to 8,000 Hz. An excitingforce and an acceleration waveform at this point were detected, therebyperforming a damping test of the laminate (laminated glass) 3 or 4 bythe central exciting method.

A mechanical impedance at an exciting point (the central portion of thelaminate to which a vibration had been given) was determined on thebasis of the obtained exciting force and a speed signal obtained byintegrating an acceleration signal; and in an impedance curve obtainedby setting the frequency on the abscissa and the mechanical impedance onthe ordinate, respectively, loss factor of the laminate (laminatedglass) 3 or 4 was calculated from the frequency expressing the peak andthe half width at half maximum.

Furthermore, by using the loss factor and the bending stiffness per unitwidth at the tertiary resonance frequency, graphs each expressing arelation between a frequency and a sound transmission loss (STL) at 20°C. were prepared in conformity of ISO 16940 (2008). The prepared graphsare shown as A in FIGS. 4 to 23 . In the drawings, the wording “330μm/100 μm/330 μm” refers to the graph of the laminate 3, and the wording“253 μm/253 μm/253 μm” refers to the graph of the laminate 4.

A coincidence critical frequency (frequency at which a lowering of STLstarts to occur due to the coincidence effect) was determined from eachof the obtained graphs of STL.

In addition, the wording “(STL calculated from the mass law (in the caseof supposing that no coincidence effect is present) at the frequency(coincidence frequency) at which the STL is most lowered due to thecoincidence effect)−(actual STL)” was defined as ΔSTL. It may be saidthat as the ΔSTL is smaller, the lowering of STL to be caused due to thecoincidence effect can be more likely suppressed, so that the loweringof the sound insulation properties can be effectively suppressed. STLcalculated from the mass law is corresponding to STL when the lossfactor is 1 in ISO 16940 (2008).

TABLE 3 Example 1 2 3 4 5 6 7 8 9 Hydrogenated block copolymer usedTPE-1 TPE-2 TPE-3 TPE-4 TPE-5 TPE-6 TPE-7 TPE-8 TPE-9 PhysicalStructural unit of polymer block (A) St St St St St St St St Stproperties of Components constituting Ip Ip/St Ip Ip Ip Ip/Bd Bd Ip/BdIp hydrogenated polymer block (B) block Mass ratio of components 10082.5/17.5 100 100 100 56/44 100 56/44 100 copolymer constituting polymerblock (B) used Molar ratio of components 100 88/12 100 100 100 50/50 10050/50 100 in X layer constituting polymer block (B) Polymer structureA/B/A A/B/A A/B/A A/B/A A/B/A A/B/A A/B/A A/B/A A/B/A Content of polymerblock 4 4 4 8 12 12 12 12 20 (A) (% by mass) Morphology of hydrogenatedSphere Sphere Sphere Sphere Sphere Sphere Sphere Sphere Cylinder blockcopolymer Weight average molecular weight 373,000 385,000 368,000210,000 175,000 163,000 172,000 160,000 103,000 of hydrogenated blockcopolymer Hydrogenation rate 92 90 90 91 91 92 99 95 88 in polymer block(B) (mol %) Average methylene chain length 1.9 1.7 2 1.8 1.8 2.3 2.2 3.21.8 in polymer block (B) Average substituent constant 0.46 0.48 0.430.46 0.46 0.37 0.35 0.29 0.47 of side chain in polymer block (B) Vinylbond amount 57 60 50 58 58 64 77 47 60 in polymer block (B) (mol %) Peaktop temperature of tanδ (° C.) −11.1 3 −20 −10 −8.5 −21 −34.3 −38.3 −4.5Peak top intensity of tanδ 2.7 2.4 2.4 2.6 2.5 2.2 2.1 1.9 2.2 G' at((peak top temperature of tanδ) + 0.4 0.4 0.4 0.4 0.4 0.7 0.6 0.9 0.630° C.) (MPa) Minimum value of d(G′)/dTemp. −46 −41 −40 −45 −44 −39 −31−32 −36 (MPa/° C.) Shrinkage factor in MD direction (%) 2.4 2.5 2.3 2.65.1 5.1 5.3 5.2 17.6 Shear storage modulus G′ of Y layer (MPa) 43.2 43.243.2 43.2 43.2 43.2 43.2 43.2 43.2 Physical I value (330 μm/100 μm/330μm) 37,100 2,430 113,000 32,400 28,500 138,000 649,000 1,470,000 10,200properties of Peak top frequency of tanδ 8,300 450 32,400 7,500 6,76040,000 180,000 430,000 1,780 laminate 3 of hydrogenated block copolymer(Hz) Bending stiffness B 198 287 120 185 173 117 126 114 331 per unitwidth (Pa·m³) (330 μm/100 μm/330 μm) Surface density m (kg/m²) 9.9 9.89.8 9.9 9.7 9.8 9.7 9.8 10.0 (330 μm/100 μm/330 μm) Coincidence criticalfrequency 4100 3400 5300 4300 4400 5300 5100 5400 3200 (330 μm/100μm/330 μm) STL(dB) (4,000 Hz, 38.6 33.5 40.3 38.1 40.3 41.7 41.2 41.728.8 (330 μm/100 μm/330 μm)) STL (dB) (6,300 Hz, 42.7 42.5 42.5 44.945.3 40.1 38.0 35.9 46.0 (330 μm/100 μm/330 μm)) ΔSTL (330 pm/100 pm/330pm) 9.4 9.1 7.3 5.3 5.2 9.7 11.7 13.9 13.8 Physical I value (253 μm/253μm/253 μm) 33,500 2,300 101,000 30,700 28,100 121,000 545,000 1,330,0008,240 properties of Peak top frequency of tanδ 8,300 450 32,400 7,5006,760 40,000 180,000 430,000 1,780 laminate 4 of hydrogenated blockcopolymer (Hz) Bending stiffness B 158 256 95 165 171 90 90 95 211 perunit width (Pa·m³) (253 μm/253 μm/253 μm) Surface density m (kg/m²) 9.79.8 9.8 9.9 9.9 9.9 9.8 9.9 9.9 (253 μm/253 μm/253 μm) Coincidencecritical frequency 4600 3600 5900 4500 4400 6100 6100 5900 4000 (253μm/253 μm/253 μm) STL (dB) (4,000 Hz, 39.9 34.3 38.7 38.6 40.0 42.4 42.142.2 39.2 (253 μm/253 μm/253 μm)) STL (dB) (6,300 Hz, 41.2 43.3 41.344.4 44.4 40.6 39.8 39.1 46.3 (253 μm/253 μm/253 μm)) ΔSTL (253 μm/253μm/253 μm) 8.6 8.3 11.1 5.8 5.9 15.1 15.7 18.6 5.7

TABLE 4 Example 10 11 12 13 14 15 Hydrogenated block copolymer usedTPE-10 TPE-11 TPE-12 TPE-13 TPE-14 TPE-15 Physical Structural unit ofpolymer block (A) St St St St St St properties of Componentsconstituting Ip/St Ip IB Bd/St Bd/St Ip hydrogenated polymer block (B)block Mass ratio of components 82.5/17.5 100 100 96/4 69/31 100copolymer constituting polymer block (B) used Molar ratio of components88/12 100 100 98/2 81/19 100 in X layer constituting polymer block (B)Polymer structure A/B/A A/B/A A/B/A A/B/A A/B/A A/B Content of polymerblock (A) 20 20 20 6 16 4 (% by mass) Morphology of hydrogenatedCylinder Cylinder Cylinder Sphere Cylinder Sphere block copolymer Weightaverage molecular weight 121,000 135,000 80,000 269,000 127,000 375,000of hydrogenated block copolymer Hydrogenation rate 90 85 — 98 98 92 inpolymer block (B) (mol %) Average methylene chain length 1.7 1.5 1 2.54.8 1.9 in polymer block (B) Average substituent constant 0.48 0.55 1.040.32 0.19 0.46 of side chain in polymer block (B) Vinyl bond amount 5774 — 72 40 57 in polymer block (B) (mol %) Peak top temperature of tanδ(° C.) 3.1 22.4 −34.9 −27.6 −30.2 −10.4 Peak top intensity of tanδ 2.11.6 1.39 1.39 1.29 2.6 G′ at ((peak top temperature of tanδ) + 1.0 0.61.0 0.6 1.3 0.4 30° C.) (MPa) Minimum value of d(G′)/dTemp. −45 −25 −25−15 −25 −44 (MPa/° C.) Shrinkage factor in MD direction (%) 19.5 18.518.8 2.6 15.8 2.4 Shear storage modulus G′ of Y layer (MPa) 43.2 43.243.2 43.2 43.2 43.2 Physical I value (330 μm/100 μm/330 μm) 2,280 551,140 234,680 1,439,610 45,380 properties of Peak top frequency of tanδof 380 0.9 15,670 62,220 400,000 9,000 laminate 3 hydrogenated blockcopolymer (Hz) Bending stiffness B 352 360 104 139 127 239 per unitwidth (Pa·m³) (330 μm/100 μm/330 μm) Surface density m (kg/m²) 9.8 9.89.8 9.8 9.8 9.4 (330 μm/100 μm/330 μm) Coincidence critical frequency3100 3000 5600 4900 5100 3600 (330 μm/100 μm/330 μm) STL (dB) (4,000 Hz,24.9 30.5 40.7 38.5 39.3 35.5 (330 μm/100 μm/330 μm)) STL(dB) (6,300 Hz,44.0 38.7 36.6 36.8 35.2 45.2 (330 μm/100 μm/330 μm)) ΔSTL (330 μm/100μm/330 μm) 17.7 15.3 13.2 14.0 14.6 8.8 Physical I value (253 μm/253μm/253 μm) 2,240 5 42,000 204,760 1,234,940 42,010 properties of Peaktop frequency of tanδ of 380 0.9 15,670 62,220 400,000 9,000 laminate 4hydrogenated block copolymer (Hz) Bending stiffness B 340 332 100 106 93207 per unit width (Pa·m³) (253 μm/253 μm/253 μm) Surface density m(kg/m²) 9.8 9.8 9.8 9.8 9.8 9.5 (253 μm/253 μm/253 μm) Coincidencecritical frequency 3100 3200 5800 5600 6000 3900 (253 μm/253 μm/253 μm)STL (dB) (4,000 Hz, 31.4 30.3 42.2 40.6 41.2 37.7 (253 μm/253 μm/253μm)) STL (dB) (6,300 Hz, 47.9 37.5 39.2 33.6 31.1 44.3 (253 μm/253μm/253 μm)) ΔSTL (253 μm/253 μm/253 μm) 11.2 15.3 15.5 16.1 18.7 8.5Example Comparative Example 16 1 2 3 4 5 Hydrogenated block copolymerused TPE-16 TPE-1' TPE-2' TPE-3' TPE-4 TPE-5' Physical Structural unitof polymer block (A) St St St St St St properties of Componentsconstituting Ip/St Ip/Bd Bd Bd/St Ip Ip hydrogenated polymer block (B)block Mass ratio of components 75/25 56/44 100 11/89 100 100 copolymerconstituting polymer block (B) used Molar ratio of components 82/1850/50 100 20/80 100 100 in X layer constituting polymer block (B)Polymer structure A/B/A A/B/A A/B/A A/B/A A/B/A A/B/A Content of polymerblock (A) 4 30 30 30 0.5 33 (% by mass) Morphology of hydrogenatedSphere Cylinder Cylinder Cylinder — Cylinder block copolymer Weightaverage molecular weight 390,000 92,000 77,000 100,000 380,000 310,000of hydrogenated block copolymer Hydrogenation rate 90 98 98 98 90 90 inpolymer block (B) (mol %) Average methylene chain length 1.7 6.4 7 1.51.8 1.8 in polymer block (B) Average substituent constant 0.48 0.15 0.130.55 0.47 0.46 of side chain in polymer block (B) Vinyl bond amount 58 638 40 60 58 in polymer block (B) (mol %) Peak top temperature of tanδ (°C.) 8.4 −49.5 −47 60 — -8.9 Peak top intensity of tanδ 2.4 0.4 0.4 0.2 —0.98 G′ at ((peak top temperature of tanδ) + 0.6 9.4 14 20 — 14 30° C.)(MPa) Minimum value of d(G′)/dTemp. −45 −22 −16 −10 — -7 (MPa/° C.)Shrinkage factor in MD direction (%) 2.7 16.8 17.2 19.5 — 20.3 Shearstorage modulus G′ of Y layer (MPa) 43.3 43.2 43.2 43.2 — 43.2 PhysicalI value (330 μm/100 μm/330 μm) 180 28,900,000,000 540,000,000 0.0896 —15,700 properties of Peak top frequency of tanδ of 30 7,830,000,000142,000,000 0.0150 — 2,600 laminate 3 hydrogenated block copolymer (Hz)Bending stiffness B 323 135 140 350 — 350 per unit width (Pa·m³) (330μm/100 μm/330 μm) Surface density m (kg/m²) 9.5 9.9 9.7 9.8 — 9.6 (330μm/100 μm/330 μm) Coincidence critical frequency 3200 5000 4800 3100 —3000 (330 μm/100 μm/330 μm) STL (dB) (4,000 Hz, 26.3 38.7 38.3 26.8 —31.0 (330 μm/100 μm/330 μm)) STL(dB) (6,300 Hz, 36.0 31.6 31.9 36.4 —39.5 (330 μm/100 μm/330 μm)) ΔSTL (330 μm/100 μm/330 μm) 16.3 19.3 20.118.8 — 14.4 Physical I value (253 μm/253 μm/253 μm) 180 25,000,000,000462,000,000 0.09 — 14,110 properties of Peak top frequency of tanδ of 307,830,000,000 142,000,000 0.015 — 2,600 laminate 4 hydrogenated blockcopolymer (Hz) Bending stiffness B 330 100 105 340 — 280 per unit width(Pa·m³) (253 μm/253 μm/253 μm) Surface density m (kg/m²) 9.7 9.8 9.9 9.8— 9.5 (253 μm/253 μm/253 μm) Coincidence critical frequency 3200 58005600 3100 — 3400 (253 μm/253 μm/253 μm) STL (dB) (4,000 Hz, 31.7 40.940.6 26.8 — 30.4 (253 μm/253 μm/253 μm)) STL (dB) (6,300 Hz, 40.4 28.929.4 34.4 — 39.8 (253 μm/253 μm/253 μm)) ΔSTL (253 μm/253 μm/253 μm)12.0 20.9 20.4 18.5 — 12.2<Description of Abbreviations in Tables 3 and 4>

St: Styrene

Bd: Butadiene

Ip: Isoprene

IB: Isobutylene

As is clear from the results shown in Tables 3 and 4 and FIGS. 4 to 23 ,in Examples 1 to 16, a plenty of products are small in the shrinkagefactor in the MD direction of the intermediate film for laminated glass(also low in the shrinking properties) and large in the peak topintensity of tan δ as compared with Comparative Examples 1 to 3 and 5.Furthermore, with respect to the laminates 3 and 4, in a plenty of theExamples, the I value falls within the range of from 200 to 2,000,000,and therefore, the coincidence critical frequency and the peak topfrequency of tan δ exhibit a value close to each other, and it is notedthat the lowering of the sound insulation properties due to a loweringof STL to be caused due to the coincidence effect is effectivelysuppressed. In particular, in Examples 1 to 5, 9, and 15, the loweringof the sound insulation properties due to a lowering of STL to be causeddue to the coincidence effect is more effectively suppressed.

In addition, in Examples 3, 6 to 8, and 12 to 14, the coincidencecritical frequency is increased, and it may be said that the soundinsulation properties in a low frequency region (for example, 4,000 Hzor less) is much more excellent.

INDUSTRIAL APPLICABILITY

The hydrogenated block copolymer of the present invention is able toenhance the sound insulation properties in laminated glasses of anythickness, and therefore, it is useful as a vibration damping material,a sound insulator, an intermediate film for laminated glass, a damrubber, a shoe sole material, a flooring material, and so on.Furthermore, the hydrogenated block copolymer of the present inventioncan also be used for weather strip, a floor mat, and so on.

In addition, the hydrogenated block copolymer of the present inventioncan be utilized for a sealing material, an adhesive, apressure-sensitive adhesive, a packing material, an O-ring, a belt, asoundproof material, and so on in various recorders in the field ofhousehold electrical appliance, such as a Blu-ray recorder and an HDDrecorder; and in various electrical products, such as a projector, agame player, a digital camera, a home video recorder, an antenna, aspeaker, an electronic dictionary, an IC recorder, a fax machine, acopying machine, a telephone, an intercom, a rice cooker, a microwaveoven, a multifunction microwave oven, a refrigerator, a dishwasher, adish dryer, an IH cooking heater, a hot plate, a vacuum cleaner, awashing machine, a battery charger, a sewing machine, an iron, a drier,a power-assisted bicycle, an air cleaner, a water purifier, an electrictoothbrush, lighting equipment, an air conditioner, an outdoor unit ofair conditioner, a dehumidifier, and a humidifier.

REFERENCE SIGNS LIST

-   -   1: Polymer block (A)    -   2: Polymer block (B)

The invention claimed is:
 1. A laminate, comprising: an X layercomprising a hydrogenated block copolymer; and a plurality of Y layerslaminated on at least one surface of the X layer; wherein thehydrogenated block copolymer is a hydrogenation product of a blockcopolymer comprising a polymer block (A) consisting of a structural unitderived from an aromatic vinyl compound and a polymer block (B)containing 30 mol % or more of a structural unit derived from at leastone selected from the group consisting of a conjugated diene compoundand isobutylene, when the polymer block (B) is regarded as having astructure with a hydrogenation rate of 100 mol %, an average value of amethylene chain length of a main chain of the structural unit derivedfrom at least one selected from the group consisting of a conjugateddiene compound and isobutylene is from 1.0 to 6.0; wherein at least oneof the plural Y layers is a layer comprising a thermoplastic resin(different from the hydrogenated block copolymer, and the thermoplasticresin (i) is an ionomer or a polyvinyl acetal resin.
 2. The laminateaccording to claim 1, wherein the content of the polymer block (A) theblock copolymer is from 1 to 30% by mass.
 3. The laminate according toclaim 1, wherein the hydrogenation rate in the polymer block (B) is from80 to 99 mol %.
 4. The laminate according to claim 1, wherein theaverage value of a methylene chain length of a main chain of thestructural unit derived from the conjugated diene compound andisobutylene is from 1.5 to 3.0.
 5. The laminate according to claim 1,wherein when the polymer block (B) has a structure with a hydrogenationrate of 100 mol %, an average value of a substituent constant (v) of aside chain which the main chain has per ethylene unit is from 0.25 to1.1.
 6. The laminate according to claim 1, wherein the polymer block (B)comprises a conjugated diene compound and the conjugated diene compoundis isoprene.
 7. The laminate according to claim 1, wherein a weightaverage molecular weight (Mw) of the polymer block (A) is from 3,000 to60,000.
 8. The laminate according to claim 1, wherein a weight averagemolecular weight (Mw) of the polymer block (B) is from 15,000 to800,000.
 9. The laminate according to claim 1, wherein a weight averagemolecular weight (Mw) of the hydrogenated block copolymer is from 15,000to 800,000.
 10. The laminate according to claim 1, wherein a bondingmode of the polymer block (A) and the polymer block (B) is selected fromthe group consisting of A-B, A-B-A, B-A-B, A-B-A-B, A-B-A-B-A, B-A-B-A-Band (A-B)n-X, wherein A represents polymer block (A), B representspolymer block (B), n is an integer of 3 or more and X represents acoupling agent residue.
 11. The laminate according to claim 1, whereinat least one of the plurality of Y layers is a glass layer.
 12. Thelaminate according to claim 1, wherein at least one of the plurality ofY layers is a polyvinyl acetal resin.
 13. The laminate according toclaim 1, comprising, in the order listed: a glass layer, a layercontaining the thermoplastic resin (i), the X layer, a layer containingthe thermoplastic resin (i), and a glass layer.
 14. An intermediate filmfor laminated glass, comprising the laminate according to claim
 1. 15.The intermediate film for laminated glass according to claim 14,comprising the hydrogenated block copolymer, wherein a peak toptemperature of tan δ, as measured with respect to a sheet-shaped testpiece having a thickness of 1.0 mm, which is obtained by molding thecopolymer according to the following molding condition, under acondition at a strain amount of 0.1%, a frequency of 1 Hz, a measurementtemperature of −70 to 200° C., and a temperature rise rate of 3° C./minin conformity of HS K7244-10 (2005) is −40 to 35° C.: Molding condition:to apply a pressure at a temperature of 230° C. under a pressure of 10MPa for 3 minutes.
 16. The laminate according to claim 1, wherein atleast one of the plurality of Y layers is an ionomer.